Multiple catalyst system for olefin polymerization and polymers produced therefrom

ABSTRACT

This invention relates to a polymer comprising one or more C3 to C40 olefins, optionally one or more diolefins, and less than 15 mole % of ethylene, where the polymer has:  
     a) a Dot T-Peel of 1 Newton or more; and  
     b) a branching index (g′) of 0.95 or less measured at the Mz of the polymer;  
     c) an Mw of 100,000 or less.  
     This invention also relates a polymer comprising one or more C3 to C40 olefins where the polymer has:  
     a) a Dot T-Peel of 1 Newton or more on Kraft paper;  
     b) a branching index (g′) of 0.95 or less measured at the Mz of the polymer;  
     c) a Mw of 10,000 to 100,000; and  
     d) a heat of fusion of 1 to 70 J/g.  
     This invention also relates a polymer comprising one or more C3 to C40 olefins where the polymer has:  
     a) a Dot T-Peel of 1 Newton or more on Kraft paper;  
     b) a branching index (g′) of 0.98 or less measured at the Mz of the polymer;  
     c) a Mw of 10,000 to 60,000;  
     d) a heat of fusion of 1 to 50 J/g.  
     This invention also relates to a homopolypropylene or a copolymer of propylene and up to 5 mole % ethylene having:  
     a) an isotactic run length of 1 to 30 (isotactic run length “IRL” is defined to be the percent of mmmm pentad divided by 0.5×percent of mmmr pentad) as determined by Carbon 13 NMR, preferably 3 to 25, more preferably 4 to 20,  
     b) a percent of r dyad of greater than 20%, preferably from 20 to 70% as determined by Carbon 13 NMR, and  
     c) a heat of fusion of 70 J/g or less, preferably 60 J/g or less, more preferably between 1 and 55 J/g, more preferably between 4 and 50 J/g.  
     This invention further relates to a process to produce an olefin polymer comprising:  
     1) selecting a first catalyst component capable of producing a polymer having an Mw of 100,000 or less and a crystallinity of 5% or less at selected polymerization conditions;  
     2) selecting a second catalyst component capable of producing polymer having an Mw of 100,000 or less and a crystallinity of 20% or more at the selected polymerization conditions;  
     3) contacting the catalyst components in the presence of one or more activators with one or more C3 to C40 olefins, at the selected polymerization conditions in a reaction zone;  
     4) obtaining the polymer.  
     This invention further relates to a continuous process to produce a branched olefin polymer comprising:  
     1) selecting a first catalyst component capable of producing a polymer having an Mw of 100,000 or less and a crystallinity of 5% or less under selected polymerization conditions;  
     2) selecting a second catalyst component capable of producing polymer having an Mw of 100,000 or less and a crystallinity of 20% or more at the selected polymerization conditions;  
     3) contacting the catalyst components in the presence of one or more activators with one or more C3 to C40 olefins, and, optionally one or more diolefins;  
     4) at a temperature of greater than 100° C.;  
     5) at a residence time of 120 minutes or less;  
     6) wherein the ratio of the first catalyst to the second catalyst is from 1:1 to 50:1;  
     7) wherein the activity of the catalyst components is at least 100 kilograms of polymer per gram of the catalyst components; and wherein at least 20% of the olefins are converted to polymer.

RELATED CASE INFORMATION

[0001] This application claims priority to provisional U.S. S. No.60/418,482, filed Oct. 15, 2002, entitled “Multiple Catalyst System forOlefin Polymerization and Polymers Produced Therefrom.” This applicationalso claims priority from U.S. S. No. 60/460,714, filed Apr. 4, 2003entitled “Polyolefin Adhesive Compositions and Articles Made Therefrom.”

[0002] This application is related to U.S. S. No. 60/199,093, filed onApr. 21, 2000 and US2000000199093P, filed Apr. 20, 2001 claimingpriority from U.S. S. No. 60/199,093. The instant application alsorelates to U.S. S. No. 60/171,715, filed Dec. 21, 1999; U.S. Ser. No.09/745,394, filed Dec. 21, 2000; and U.S. Ser. No. 09/746,332 filed Dec.21, 2000. The instant application also relates to WO 01/81493.

FIELD OF THE INVENTION

[0003] This invention relates to a process to polymerize olefins usingmultiple catalysts and polymers produced therefrom. In particular thisinvention relates to a process to produce polyolefin adhesives and theadhesives so produced.

BACKGROUND OF THE INVENTION

[0004] For some applications such as adhesives individual polymers donot possess the necessary combination of properties. Individualpolyolefins having certain characteristics are often blended together inthe hope of combining the positive attributes of the individualcomponents. Typically the result is a blend which displays an average ofthe individual properties of the individual resins. For example EP 0 527589 discloses blends of flexible, low molecular weight amorphouspolypropylene with higher molecular weight isotactic polypropylene toobtain compositions with balanced mechanical strength and flexibility.These compositions show better flexibility compared to that of theisotactic polypropylene alone, but are still lacking in other physicalattributes. Physical blends also have the problems of inadequatemiscibility. Unless the components are selected for their compatibilitythey can phase separate or smaller components can migrate to thesurface. Reactor blends, also called intimate blends (a compositioncomprising two or more polymers made in the same reactor or in a seriesof reactors) are often used to address these issues, however findingcatalyst systems that will operate under the same environments toproduce different polymers has been a challenge.

[0005] Multiple catalyst systems have been used in the past to producereactor blends (also called intimate blends) of various polymers andother polymer compositions. Reactor blends and other one-pot polymercompositions are often regarded as superior to physical blends ofsimilar polymers. For example U.S. Pat. No. 6,248,832 discloses apolymer composition produced in the presence of one or morestereospecific metallocene catalyst systems and at least onenon-stereospecific metallocene catalyst system. The resultant polymerhas advantageous properties over the physical blends disclosed in EP 0527 589 and U.S. Pat. No. 5,539,056.

[0006] Thus there has been interest in the art in developing multiplecatalyst systems to produce new polymer compositions. For example, U.S.Pat. No. 5,516,848 discloses the use of two different cyclopentadienylbased transition metal compounds activated with alumoxane ornon-coordinating anions. In particular, the examples disclose, amongother things, catalyst compounds in combination, such as(Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂ and rac-Me₂Si(H₄Ind)ZrCl₂, orMe₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂ and Me₂Si(Ind₂)HfMe₂, (Ind=indenyl)activated with activators such as methylalumoxane or N,N-dimethylanilinium tetrakis(pentafluorphenyl) borate to produce polypropyleneshaving bimodal molecular weight distributions (Mw/Mn), varying amountsof isotacticity (from 12 to 52 weight % isotactic PP in the product inEx 2, 3 and 4), and having weight average molecular weights over100,000, and some even as high as 1,200,000 for use as thermoplastics.Likewise, U.S. Pat. No. 6,184,327 discloses a thermoplastic elastomercomprising a branched olefin polymer having crystalline sidechains andan amorphous backbone wherein at least 90 mole percent of the sidechainsare isotactic or syndiotactic polypropylene and at least 80 mole percentof the backbone is atactic polypropylene produced by a processcomprising: a) contacting, in solution, at a temperature from about 90°C. to about 120° C., propylene monomers with a catalyst compositioncomprising a chiral, stereorigid transition metal catalyst compoundcapable of producing isotactic or syndiotactic polypropylene; b)copolymerizing the product of a) with propylene and, optionally, one ormore copolymerizable monomers, in a polymerization reactor using anachiral transition metal catalyst capable of producing atacticpolypropylene; and c) recovering a branched olefin polymer. SimilarlyU.S. Pat. No. 6,147,180 discloses the synthesis of a thermoplasticpolymer composition, which is produced by first polymerizing monomers toproduce at least 40% vinyl terminated macromonomers and thencopolymerizing the macromonomers with ethylene. In addition U.S. Pat.No. 6,323,284 discloses a method to produce thermoplastic compositions(mixtures of crystalline and amorphous polyolefin copolymers) bycopolymerizing alpha-olefins and alpha, omega dienes using two separatecatalyst systems.

[0007] Likewise others have experimented with multiple stage processesto produce new polymer compositions. For example EP 0 366 411 disclosesa graft polymer having an EPDM backbone with polypropylene graftedthereto at one or more of the diene monomer sites through the use of atwo-step process using a different Ziegler-Natta catalyst system in eachstep. This graft polymer is stated to be useful for improving the impactproperties in blended polypropylene compositions.

[0008] Although each of the polymers described in the above referenceshas interesting combinations of properties, there remains a need for newcomposition that offer other new and different property balancestailored for a variety of end uses. In particular, it would be desirableto find a composition that is strong yet has adhesive characteristicsand the ability to be applied using adhesive technology and equipment.

[0009] For general information in this area, one may refer to:

[0010] 1. DeSouza and Casagrande, in 2001 addressed the issue of binarycatalyst systems in “Recent Advances in Olefin Polymerization UsingBinary Catalyst Systems, Macromol. Rapid Commun. 2001, 22, No. 16 (pages1293 to 1301). At page 1299 they report propylene systems that produce a“gooey” product.

[0011] 2. Studies with respect to the production of stereoblockpolypropylene by using in-situ mixtures of metallocene catalysts withdifferent stereoselectivity were recently performed by Lieber andBrintzinger in “Propene Polymerization with Catalyst Mixtures ContainingDifferent Ansa-Zirconocenes: Chain Transfer to Alkylaluminum Cocatalystsand Formation of Stereoblock Polymers”, Macromolecules 2000, 33, No.25(pages 9192-9199). Propylene polymerization reactions were performedusing metallocene catalysts H₄C₂(Flu)₂ZrCl₂,rac-Me₂Si(2-Me-4-tBu-C₅H₂)₂ZrCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂ in thepresence of either MAO (methylalumoxane) or triisobutylaluminium(Al^(i)Bu₃)/triphenylcarbenium tetrakis(perfluorophenylborate) (tritylborate) as the cocatalyst. Propylene polymerization using the mixedcatalysts, H₄C₂(Flu)₂ZrCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂ in the presenceof either MAO or AliBu₃/trityl borate produced waxy solids, which arecompletely separable into an atactic (diethyl ether-soluble) and anisotactic (insoluble) fraction. Neither fraction contained anycombination of isotactic and atactic pentad patterns indicating thatthese catalyst mixtures did not form stereoblock polymers.

[0012] 3. Aggarwal addressed the various polymers produced in“Structures and Properties of Block Polymers and Multiphase PolymerSystems: An Overview of Present Status and Future Potential”, S. L.Aggarwal, Sixth Biennial Manchester Polymer Symposium (UMIST Manchester,March 1976)

[0013] 4. “Selectivity in Propene Polymerization with MetalloceneCatalysts” Resconi, et al, Chem Rev. 2000, 100, 1253-1345.

[0014] None of the references above has directly addressed the need forpolyolefin based adhesives containing both amorphous and crystallinecomponents. Such adhesives are desired in the industry as a replacementfor blends requiring significant amount of hydrocarbon resin tackifiers.

[0015] Additional references that are of interest include:

[0016] 1) EP Patents: EP0 619 325 B1, EP719 802 B1;

[0017] 2) US Patents/Publications: U.S. Pat. Nos. 6,207,606, 6,258,903;6,271,323; 6,340,703, 6,297,301, US 2001/0007896 A1, U.S. Pat. Nos.6,184,327, 6,225,432, 6,342,574, 6,147,180, 6,114,457, 6,143,846,5,998,547; 5,696,045; 5,350,817, U.S. Pat. No. 6,569,965,

[0018] 3) PCT Publications: WO 00/37514, WO 01/81493, WO 98/49229, WO98/32784; and WO 01/09200

[0019] 4) “Metallocene-Based Branch-Block thermoplastic Elastomers,”Markel, et al. Macromolecules 2000, Volume 33, No. 23. pgs. 8541-8548.

SUMMARY OF THE INVENTION

[0020] This invention relates to a polymer comprising one or more C3 toC40 olefins, optionally one or more diolefins, and less than 15 mole %of ethylene, where the polymer has:

[0021] a) a Dot T-Peel of 1 Newton or more; and

[0022] b) a branching index (g′) of 0.95 or less measured at the Mz ofthe polymer;

[0023] c) an Mw of 100,000 or less.

[0024] This invention also relates a polymer comprising one or more C3to C40 olefins where the polymer has:

[0025] a) a Dot T-Peel of 1 Newton or more on Kraft paper;

[0026] b) a branching index (g′) of 0.95 or less measured at the Mz ofthe polymer;

[0027] c) a Mw of 10,000 to 100,000; and

[0028] d) a heat of fusion of 1 to 70 J/g.

[0029] This invention also relates a polymer comprising one or more C3to C40 olefins where the polymer has:

[0030] a) a Dot T-Peel of 1 Newton or more on Kraft paper;

[0031] b) a branching index (g′) of 0.98 or less measured at the Mz ofthe polymer;

[0032] c) a Mw of 10,000 to 60,000;

[0033] d) a heat of fusion of 1 to 50 J/g.

[0034] This invention also relates to a homopolypropylene or a copolymerof propylene and up to 5 mole % ethylene having:

[0035] a) an isotactic run length of 1 to 30 (isotactic run length “IRL”is defined to be the percent of mmmm pentad divided by 0.5×percent ofmmmr pentad) as determined by Carbon 13 NMR, preferably 3 to 25, morepreferably 4 to 20,

[0036] b) a percent of r dyad of greater than 20%, preferably from 20 to70% as determined by Carbon 13 NMR, and

[0037] c) a heat of fusion of 70 J/g or less, preferably 60 J/g or less,more preferably between 1 and 55 J/g, more preferably between 4 and 50J/g.

[0038] This invention further relates to a process to produce an olefinpolymer comprising:

[0039] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less and a crystallinity of 5% orless at selected polymerization conditions;

[0040] 2) selecting a second catalyst component capable of producingpolymer having an Mw of 100,000 or less and a crystallinity of 20% ormore at the selected polymerization conditions;

[0041] 3) contacting the catalyst components in the presence of one ormore activators with one or more C3 to C40 olefins, at the selectedpolymerization conditions in a reaction zone;

[0042] 4) obtaining the polymer.

[0043] This invention further relates to a continuous process to producea branched olefin polymer comprising:

[0044] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less and a crystallinity of 5% orless under selected polymerization conditions;

[0045] 2) selecting a second catalyst component capable of producingpolymer having an Mw of 100,000 or less and a crystallinity of 20% ormore at the selected polymerization conditions;

[0046] 3) contacting the catalyst components in the presence of one ormore activators with one or more C3 to C40 olefins, and, optionally oneor more diolefins;

[0047] 4) at a temperature of greater than 100° C.;

[0048] 5) at a residence time of 120 minutes or less;

[0049] 6) wherein the ratio of the first catalyst to the second catalystis from 1:1 to 50:1;

[0050] 7) wherein the activity of the catalyst components is at least100 kilograms of polymer per gram of the catalyst components; andwherein at least 20% of the olefins are converted to polymer.

BRIEF DESCRIPTION OF THE DRAWINGS

[0051]FIG. 1 is an illustration of complex viscosity changes with thetemperature when the samples were cooled at 10 C. per minute forExamples 12, 22 and 49.

[0052]FIG. 2 is a graphic illustration of the relationship between thebranching index, g′, and the molecular weight for polymers produced inExamples 4 and 31.

[0053]FIG. 3 is the C-13 NMR spectra of heptane soxhlet insoluble (toptrace) and hexane room temperature soluble fractions (bottom trace)extracted from Example 4.

[0054]FIG. 4 is the C-13 NMR spectra of aPP/scPP branch block relativeto scPP and aPP control. The control samples were produced using onecatalyst at a time; aPP was synthesized using a specific catalyst, whilethe scPP was produced using stereospecific catalyst. The top trace isthe aPP control sample. The middle trace is the scPP control sample andthe bottom trace is Example 4.

[0055]FIG. 5 shows the relationship between temperature and complexviscosity of the fractionated samples extracted from example 31.

[0056]FIG. 6 is the DSC trace for polymer of example 32 in Table 6.

DETAILED DESCRIPTION

[0057] For the purposes of this invention and the claims thereto and forease of reference when a polymer is referred to as comprising an olefin,the olefin present in the polymer is the polymerized form of the olefin.

[0058] In another embodiment this invention relates to a polymercomprising one or more C3 to C40 olefins, preferably propylene, and lessthan 50 mole % of ethylene, having:

[0059] a) a Dot T-Peel between 1 Newton and the 10,000 Newtons; and

[0060] b) a Mz/Mn of 2 to 200; and/or

[0061] c) an Mw of X and a g′ of Y (measured at the Mz of the polymer)according to the following Table C: TABLE C X (Mw) Y (g′) 100,000 orless, preferably 80,000 or less, 0.9 or less, preferably 70,000 or less,more preferably preferably 0.7 60,000 or less, more preferably 50,000 orless, or less more preferably 40,000 or less, more preferably 30,000Preferably or less, more preferably 20,000 or less, more preferablybetween 10,000 or less. In some embodiments X is also at least 0.5-0.97000, more preferably 10,000, more preferably at least 15,000. 75,000 orless, preferably 70,000 or less, more preferably 0.92 or less, 60,000 orless, more preferably 50,000 or less, more preferably, 0.6 preferably40,000 or less, more preferably 30,000 or or less less, more preferably20,000 or less, more preferably preferably 10,000 or less. In someembodiments A is also at least between 1000, preferably at least 2000,more preferably at least 0.4-0.6- 3000, more preferably at least 4000,more preferably at least 5000, more preferably at least 7000, morepreferably 10,000, more preferably at least 15,000. 50,000 or less, morepreferably 40,000 or less, more 0.95 or less, preferably 30,000 or less,more preferably 20,000 or less, preferably 0.7 more preferably 10,000 orless. In some embodiments A or less is also at least 1000, preferably atleast 2000, more preferably preferably at least 3000, more preferably atleast between 4000, more preferably at least 5000, more preferably0.5-0.7- at least 7000, more preferably 10,000, more preferably at least15,000. 30,000 or less, preferably 25,000 or less, more preferably 0.98or less 20,000 or less, more preferably 15,000 or less, more preferablypreferably 10,000 or less. In some embodiments A is between also atleast 1000, preferably at least 2000, more 0.7-0.98 preferably at least3000, more preferably at least 4000, more preferably at least 5000, morepreferably at least 7000, more preferably 10,000, more preferably atleast 15,000.

[0062] In another embodiment, when Mw is between 15,000 and 100,000,then g′<(10⁻¹² Mw²−10⁻⁶ Mw+1.0178).

[0063] In a some embodiments the g′ is 0.9 or less, 0.8 or less, 0.7 orless, 0.6 or less, 0.5 or less measured at the Mz of the polymer.

[0064] In another embodiment the polymer described above also has a peakmelting point (Tm) between 40 and 250° C., or between 60 and 190° C., orbetween about 60 and 150° C., or between 80 and 130° C. In someembodiments the peak melting point is between 60 and 160° C. In otherembodiments the peak melting point is between 124-140° C. In otherembodiments the peak melting temperature is between 40-130° C.

[0065] In another embodiment the polymer described above also has aviscosity (also referred to a Brookfield Viscosity or Melt Viscosity) of90,000 mPa·sec or less at 190° C. (as measured by ASTM D 3236 at 190°C.); or 80,000 or less, or 70,000 or less, or 60,000 or less, or 50,000or less, or 40,000 or less, or 30,000 or less, or 20,000 or less, or10,000 or less, or 8,000 or less, or 5000 or less, or 4000 or less, or3000 or less, or 1500 or less, or between 250 and 6000 mPa·sec, orbetween 500 and 5500 mPa·sec, or between 500 and 3000 mPa·sec, orbetween 500 and 1500 mPa·sec, and/or a viscosity of 8000 mPa·sec or lessat 160° C. (as measured by ASTM D 3236 at 160° C.); or 7000 or less, or6000 or less, or 5000 or less, or 4000 or less, or 3000 or less, or 1500or less, or between 250 and 6000 mPa·sec, or between 500 and 5500mPa·sec, or between 500 and 3000 mPa·sec, or between 500 and 1500mPa·sec. In other embodiments the viscosity is 200,000 mPa·sec or lessat 190° C., depending on the application. In other embodiments theviscosity is 50,000 mPa·sec or less depending on the applications.

[0066] In another embodiment the polymer described above also has a heatof fusion of 70 J/g or less, or 60 J/g or less, or 50 J/g or less; or 40J/g or less, or 30 J/g or less, or 20 J/g or less and greater than zero,or greater than 1 J/g, or greater than 10 J/g, or between 20 and 50 J/g.

[0067] In another embodiment the polymer described above also has aShore A Hardness (as measured by ASTM 2240) of 95 or less, 70 or less,or 60 or less, or 50 or less, or 40 or less or 30 or less, or 20 orless. In other embodiments the Shore A Hardness is 5 or more, 10 ormore, or 15 or more. In certain applications, such as packaging, theShore A Hardness is preferably 60-70.

[0068] In another embodiment the polymer of this invention has an Mz/Mnof 2 to 200, preferably 2 to 150, preferably 10 to 100.

[0069] In another embodiment the polymer described above also has aShear Adhesion Fail Temperature (SAFT—as measured by ASTM 4498) of 200°C. or less, or of 40 to 150° C., or 60 to 130° C., or 65 to 110° C., or70-80° C. In certain embodiments SAFT's of 130-140° C. are preferred.

[0070] In another embodiment the polymer described above also has a DotT-Peel of between 1 Newton and 10,000 Newtons, or 3 and 4000 Newtons, orbetween 5 and 3000 Newtons, or between 10 and 2000 Newtons, or between15 and 1000 Newtons. Dot T-Peel is determined according to ASTM D 1876,except that the specimen is produced by combining two 1 inch by 3 inch(2.54 cm×7.62 cm) Kraft paper substrate cut outs with a dot of adhesivewith a volume that, when compressed under a 500 gram weight occupiesabout 1 square inch of area (1 inch=2.54 cm). Once made all thespecimens are pulled apart in side by side testing (at a rate of 2inches per minute) by a machine that records the destructive force ofthe insult being applied. The maximum force achieved for each sampletested was recorded and averaged, thus producing the Average MaximumForce which is reported as the Dot T-Peel.

[0071] In another embodiment the polymer described above also has a settime of several days to 1 second, or 60 seconds or less, or 30 secondsor less, or 20 seconds or less, or 15 seconds or less, or 10 seconds orless, or 5 seconds or less, or 4 seconds or less, or 3 seconds or less,more or 2 seconds or less, or 1 second or less.

[0072] In another embodiment the polymer described above also has anMw/Mn of 2 to 75, or 4 to 60, or 5 to 50, or 6 to 20.

[0073] In another embodiment the polymer described above also has an Mzof 1,000,000 or less, preferably 15,000 to 1,000,000, or 20,000 to800,000, or 25,000 to 350,000.

[0074] In another embodiment the polymer described above may also have astrain at break (as measured by ASTM D-1708 at 25° C.) of 50 to 1000%,preferably 80 to 200%. In some other embodiments the strain at break is100 to 500%.

[0075] In another embodiment, the polymer described herein has a tensilestrength at break (as measured by ASTM D-1708 at 25° C.) of 0.5 MPa ormore, alternatively 0.75 MPa or more, alternatively 1.0 MPa or more,alternatively 1.5 MPa or more, alternatively 2.0 MPa or more,alternatively 2.5 MPa or more, alternatively 3.0 MPa or more,alternatively 3.5 MPa or more.

[0076] In another embodiment the polymer described above also has acrystallization point (Tc) between 20 and 110° C. In some embodimentsthe Tc is between 70 to 100° C. In other embodiments the Tc is between30 to 80° C. In other embodiments the Tc is between 20 to 50° C.

[0077] In some embodiment the polymers described above has a slope of−0.1 or less, preferably −0.15 or less, more preferably −0.25 or less inthe trace of complex viscosity versus temperature as shown in FIG. 1 (asmeasured by ARES dynamic mechanical spectrometer operating at afrequency of 10 rad/s, with a strain of 20% under a nitrogen atmosphere,and a cooling rate of 10° C./min) over the range of temperatures fromTc+10° C. to Tc+40° C. The slope is defined as a derivative of log(complex viscosity) with respect to temperature.

[0078] In another embodiment the polymer described above has a Tc thatis at least 10° C. below the Tm, preferably at least 20° C. below theTm, preferably at least 30° C. below the Tm, more preferably at least35° C. below the Tm.

[0079] In another embodiment some polymers described above have a meltindex ratio (I₁₀/I₂) of 6.5 or less, preferably 6.0 or less, preferably5.5 or less, preferably 5.0 or less, preferably 4.5 or less, preferablybetween 1 and 6.0. (I₁₀ and I₂ are measured according to ASTM 1238 D,2.16 kg, 190° C.).

[0080] In another embodiment some polymers described above have a meltindex (as determined by ASTM 1238 D,2.16 kg, 190 deg. C) of 25 dg/min ormore, preferably 50 dg/min or more, preferably 100 dg/min or more, morepreferably 200 dg/min or more, more preferably 500 dg/mn or more, morepreferably 2000 dg/min or more.

[0081] In another embodiment the polymer has a melt index of 900 dg/minor more.

[0082] In another embodiment the polymer described above has a range ofcrystallization of 10 to 60° C. wide, preferably 20 to 50° C.,preferably 30 to 45° C. in the DSC traces. In DSC traces where there aretwo or more non-overlapping peaks, then each peak has a range ofcrystallization of 10 to 60° C. wide, preferably 20 to 50° C.,preferably 30 to 45° C. in the DSC traces.

[0083] In another embodiment the polymer produced by this invention hasa molecular weight distribution (Mw/Mn) of at least 2, preferably atleast 5, preferably at least 10, even more preferably at least 20.

[0084] In another embodiment the polymer produced may have a unimodal,bimodal, or multimodal molecular weight distribution (Mw/Mn)distribution of polymer species as determined by Size ExclusionChromatography (SEC). By bimodal or multimodal is meant that the SECtrace has more than one peak or inflection points. An inflection pointis that point where the second derivative of the curve changes in sign(e.g., from negative to positive or vice versus).

[0085] In another embodiment the polymer described above has an Energyof activation of 8 to 15 cal/mol Energy of activation was calculatedusing the relationships of complex viscosity and temperature over theregion where thermal effects are responsible for viscosity increase(assuming an Arrhenius-like relationship).

[0086] In another embodiment the polymers of this invention may have acrystallinity of at least 5%.

[0087] In another embodiment the polymer described above may also haveone or more of the following:

[0088] a) a peak melting point between 60 and 190° C., or between about60 and 150° C., or between 80 and 130° C.; and/or

[0089] b) a viscosity of 8000 mPa·sec or less at 190° C. (as measured byASTM D 3236 at 190° C.); or 5000 or less, or 4000 or less, or 3000 orless, or 1500 or less, or between 250 and 6000 mPa·sec, or between 500and 5500 mPa·sec, or between 500 and 3000 mPa·sec, or between 500 and1500 mPa·sec, or a viscosity of 8000 mPa·sec or less at 160° C. (asmeasured by ASTM D 3236 at 160° C.); or 7000 or less, or 6000 or less,or 5000 or less, or 4000 or less, or 3000 or less, or 1500 or less, orbetween 250 and 6000 mPa·sec, or between 500 and 5500 mPa·sec, orbetween 500 and 3000 mPa·sec, or between 500 and 1500 mPa·sec; and/or

[0090] c) an Hf(Heat of fusion) of 70 J/g or less, or 60 J/g or less, or50 J/g or less; or 40 J/g or less, or 30 J/g or less, or 20 J/g or lessand greater than zero, or greater than 1 J/g, or greater than 10 J/g, orbetween 20 and 50 J/g; and or

[0091] d) a Shore A Hardness (as measured by ASTM 2240) of 90 or less,or 80 or less, or 70 or less, or 60 or less or 50 or less, or 40 orless; and or

[0092] e) a Shear Adhesion Fail Temperature (SAFT—as measured by ASTM4498) of 40 to 150° C., or 60 to 130° C., or 65 to 110° C., or 70-80°C.; and or;

[0093] f) a Dot T-Peel of between 1 Newton and 10,000 Newtons, or 3 and4000 Newtons, or between 5 and 3000 Newtons, or between 10 and 2000Newtons, or between 15 and 1000 Newtons; and/or

[0094] g) a set time of several days to 0.1 second, or 60 seconds orless, or 30 seconds or less, or 20 seconds or less, or 15 seconds orless, or 10 seconds or less, or 5 seconds or less, or 4 seconds or less,or 3 seconds or less, more or 2 seconds or less, or 1 second or less;and or

[0095] h) an Mw/Mn of greater than 1 to 75, or 2 to 60, or 2 to 50, or 3to 20; and/or

[0096] i) an Mz of 1,000,000 or less, preferably 15,000 to 500,000, or20,000 to 400,000, or 25,000 to 350,000.

[0097] Useful combinations of features include polymers as describedabove having a Dot T-Peel of between 1 Newton and 10,000 Newtons, or 3and 4000 Newtons, or between 5 and 3000 Newtons, or between 10 and 2000Newtons, or between 15 and 1000 Newtons and:

[0098] 1. an Mw of 30,000 or less, a peak melting point between 60 and190° C., a Heat of fusion of 1 to 70 J/g, a branching index (g′) of 0.90or less measured at the Mz of the polymer; and a melt viscosity of 8000mPa·sec or less at 190° C.; or

[0099] 2. an Mz of 20,000 to 500,000 and a SAFT of 60 to 150° C.; or

[0100] 3. an Mz/Mn of 2-200 and a set time of 2 seconds or less; or

[0101] 4. an Hf (heat of fusion) of 20 to 50 J/g, an Mz or20,000-500,000 and a shore hardness of 50 or less; or

[0102] 5. an Mw/Mn of greater than 1 to 50, a viscosity of 5000 or lessmPa·sec at 190° C.; or

[0103] 6. an Mw of 50,000 or less, a peak melting point between 60 and190° C., a heat of fusion of 2 to 70 J/g, a branching index (g′) of 0.70or less measured at the Mz of the polymer, and a melt viscosity of 8000mPa·sec or less at 190° C.

[0104] In a preferred embodiment, the polymer of this inventioncomprises amorphous, crystalline and branch-block molecular structures.

[0105] In a preferred embodiment the polymer comprises at least 50weight % propylene, preferably at least 60% propylene, alternatively atleast 70% propylene, alternatively at least 80% propylene. In anotherembodiment the polymer comprises propylene and 15 mole % ethylene orless, preferably 10 mole % ethylene or less, more preferably 9 mole %ethylene or less, more preferably 8 mole % ethylene or less, morepreferably 7 mole % ethylene or less, more preferably 6 mole % ethyleneor less, more preferably 5 mole % ethylene or less, more preferably 4mole % ethylene or less, more preferably 3 mole % ethylene or less, morepreferably 2 mole % ethylene or less, more preferably 1 mole % ethyleneor less.

[0106] In another embodiment the polymer of this invention comprisesless than 5 mole % of ethylene, preferably less than 4.5 mole %ethylene, preferably less than 4.0 mole % ethylene, alternatively lessthan 3.5 mole % ethylene, alternatively less than 3.0 mole % ethylene,alternatively less than 2.5 mole % ethylene, alternatively less than 2.0mole % ethylene, alternatively less than 1.5 mole % ethylene,alternatively less than 1.0 mole % ethylene, alternatively less than 0.5mole % ethylene, alternatively less than 0.25 mole % ethylene,alternatively 0 mole % ethylene.

[0107] In another embodiment the polymer produced has a glass transitiontemperature (Tg) as measured by ASTM E 1356 of 5° C. or less, preferably0° C. or less, preferably −5° C. or less, alternatively between −5° C.and −40° C., alternatively between −5° C. and −15° C.

[0108] In another embodiment the polymer of this invention has anamorphous content of at least 50%, alternatively at least 60%,alternatively at least 70%, even alternatively between 50 and 99%.Percent amorphous content is determined using Differential ScanningCalorimetry measurement according to ASTM E 794-85.

[0109] In another embodiment the polymer of this invention has acrystallinity of 40% or less, alternatively 30% or less, alternatively20% or less, even alternatively between 10% and 30%. Percentcrystallinity content is determined using Differential ScanningCalorimetry measurement according to ASTM E 794-85. In anotherembodiment, the polymers described herein have a percent crystallinityof between 5 and 40%, alternatively between 10 to 30%.

[0110] In another embodiment the polymer produced by this invention hasa molecular weight distribution (Mw/Mn) of at least 1.5, preferably atleast 2, preferably at least 5, preferably at least 10, evenalternatively at least 20. In other embodiments the Mw/Mn is 20 or less,10 or less, even 5 or less. Molecular weight distribution generallydepends on the catalysts used and process conditions such astemperature, monomer concentration, catalyst ratio, if multiplecatalysts are used, and the presence or absence of hydrogen. Hydrogenmay be used at amounts up to 2 weight %, but is preferably used atlevels of 50 to 500 ppm.

[0111] In another embodiment the polymer produced is found to have atleast two molecular weights fractions are present at greater than 2weight %, preferably greater than 20 weight %, each based upon theweight of the polymer as measured by Gel Permeation Chromatography. Thefractions can be identified on the GPC trace by observing two distinctpopulations of molecular weights. An example would be a GPC traceshowing a peak at 20,000 Mw and another peak at 50,000 Mw where the areaunder the first peak represents more than 2 weight % of the polymer andthe area under the second peak represents more than 2 weight % of thepolymer.

[0112] In another embodiment the polymer of this invention has 20 weight% or more (based upon the weight of the starting polymer) of hexane roomtemperature soluble fraction, and 70 weight % or less, preferably 50weight % or less of Soxhlet boiling heptane insolubles, based upon theweight of the polymer. Soxhlet heptane insoluble refers to one of thefractions obtained when a sample is fractionated using successivesolvent extraction technique. The fractionations are carried out in twosteps: one involves room temperature solvent extraction, the othersoxhlet extraction. In the room temperature solvent extraction, aboutone gram of polymer is dissolved in 50 ml of solvent (e.g., hexane) toisolate the amorphous or very low molecular weight polymer species. Themixture is stirred at room temperature for about 12 hours. The solublefraction is separated from the insoluble material using filtration undervacuum. The insoluble material is then subjected to a Soxhlet extractionprocedure. This involves the separation of polymer fractions based ontheir solubility in various solvents having boiling points from justabove room temperature to 110° C. The insoluble material from the roomtemperature solvent extraction is first extracted overnight with asolvent such as hexane and heptane (Soxhlet); the extracted material isrecovered by evaporating the solvent and weighing the residue. Theinsoluble sample is then extracted with a solvent having higher boilingtemperature such as heptane and after solvent evaporation, it isweighed. The insolubles and the thimble from the final stage areair-dried in a hood to evaporate most of the solvent, then dried in anitrogen-purged vacuum oven. The amount of insoluble left in the thimbleis then calculated, provided the tare weight of the thimble is known.

[0113] In another embodiment, the polymers produced in this inventionhave a heptane insoluble fraction 70 weight % or less, based upon theweight of the starting polymer, and the heptane insoluble fraction hasbranching index g′ of 0.9 (preferably 0.7) or less as measured at the Mzof the polymer. In a preferred embodiment the composition also has atleast 20 weight % hexane soluble fraction, based upon the weight of thestarting polymer. In another embodiment, the polymers produced in thisinvention have a heptane insoluble fraction 70 weight % or less, basedupon the weight of the starting polymer and a Mz between 20,000 and5000,000 of the heptane insoluble portion. In a preferred embodiment thecomposition also has at least 20 weight % hexane soluble fraction, basedupon the weight of the starting polymer. In another embodiment thepolymers produced have a hexane soluble portion of at least 20 weight %,based upon the weight of the starting polymer.

[0114] In another embodiment the polymer comprises propylene and 15 mole% ethylene or less, preferably 10 mole % ethylene or less, morepreferably 9 mole % ethylene or less, more preferably 8 mole % ethyleneor less, more preferably 7 mole % ethylene or less, more preferably 6mole % ethylene or less, more preferably 5 mole % ethylene or less, morepreferably 4 mole % ethylene or less, more preferably 3 mole % ethyleneor less, more preferably 2 mole % ethylene or less, more preferably 1mole % ethylene or less.

[0115] In another embodiment the polymer of this invention comprisesless than 5 mole % of ethylene, preferably less than 4.5 mole %ethylene, preferably less than 4.0 mole % ethylene, alternatively lessthan 3.5 mole % ethylene, alternatively less than 3.0 mole % ethylene,alternatively less than 2.5 mole % ethylene, alternatively less than 2.0mole % ethylene, alternatively less than 1.5 mole % ethylene,alternatively less than 1.0 mole % ethylene, alternatively less than 0.5mole % ethylene, alternatively less than 0.25 mole % ethylene,alternatively 0 mole % ethylene.

[0116] For ease of reference the polymer produced by the second catalysthaving at least 20% crystallinity may also be referred to as the“semi-crystalline polymer” and the polymer produced by the firstcatalyst component having a crystallinity of less than 5% may bereferred to as the “amorphous polymer.”

[0117] In another embodiment of this invention the polymer produced hasa characteristic three-zone complex viscosity-temperature pattern, asshown in FIG. 1. The temperature dependence of complex viscosity wasmeasured using ARES dynamic mechanical spectrometer operating at afrequency of 10 rad/s, with a strain of 20% under a nitrogen atmosphere,and a cooling rate of 10° C./min. The sample was first molten thengradually cooled down to room temperature while monitoring the build-upin complex viscosity. Above the melting point, which is typical ofpolymer processing temperature, the complex viscosity is relatively low(Zone I) and increases gradually with decreasing temperature. In zoneII, a sharp increase in complex viscosity appears as temperature isdropped. The third zone (Zone III) is the high complex viscosity zone,which appears at lower temperatures corresponding to application (enduse) temperatures. In Zone III the complex viscosity is high and variesslightly with further decrease in temperature. Such a complex viscosityprofile provides, in hot melt adhesive applications, a desirablecombination of long opening time at processing temperatures and fast settime at lower temperatures.

[0118] In a preferred embodiment, the polymers produced herein havingless than 1 mol % ethylene, have at least 2 mol % (CH₂)₂ units,preferably 4 mol %, preferably 6 mol %, more preferably 8 mol %, morepreferably 10 mol %, more preferably 12 mol %, more preferably 15 mol %,more preferably 18 mol %, more preferably 5 mol % as measured by Carbon13 NMR as described below.

[0119] In an another embodiment, the polymers produced herein havingbetween 1 and 10 mol % ethylene, have at least 2+X mol % (CH₂)₂ units,preferably 4+X mol %, preferably 6+X mol %, more preferably 8+X mol %,more preferably 10+X mol %, more preferably 12+X mol %, more preferably15+X mol %, more preferably 18+X mol %, more preferably 20+X mol %,where X is the mole % of ethylene, and the (CH₂)₂ units are determinedby Carbon 13 NMR as described below.

[0120] In a preferred embodiment, the polymers produced herein, havingless than 1 mol % ethylene, have an amorphous component (which isdefined to be that portion of the polymer composition that has acrystallinity of less than 5%) which contains at least 3 mol % (CH₂)₂units, preferably 4 mol %, preferably 6 mol %, more preferably 8 mol %,more preferably 10 mol %, more preferably 12 mol %, more preferably 15mol %, more preferably 18 mol %, more preferably 20 mol % as measured byCarbon 13 NMR as described below.

[0121] In an another embodiment, the polymers produced herein havingbetween 1 and 10 mol % ethylene, have an amorphous component (which isdefined to be that portion of the polymer composition that has acrystallinity of less than 20%) which contains at least 3+X mol % (CH₂)₂units, preferably 4+X mol %, preferably 6+X mol %, more preferably 8+Xmol %, more preferably 10+X mol %, more preferably 12+X mol %, morepreferably 15+X mol %, more preferably 18+X mol %, more preferably 20+Xmol %, where X is the mole % of ethylene, and the (CH₂)₂ units aredetermined by Carbon 13 NMR as described below.

[0122] Monomers

[0123] In a preferred embodiment the polymer comprises an olefinhomopolymer or copolymer, comprising one or more C3 to C40 alphaolefins. In another preferred embodiment the olefin polymer furthercomprises one or more diolefin comonomers, preferably one or more C4 toC40 diolefins.

[0124] In a preferred embodiment the polymer comprises an olefinhomopolymer or copolymer, having less than 5 mol % ethylene, andcomprising one or more C3 to C40 alpha olefins. In another preferredembodiment the olefin polymer, having less than 5 mol % ethylene,further comprises one or more diolefin comonomers, preferably one ormore C4 to C40 diolefins.

[0125] In a preferred embodiment the polymer produced herein is apropylene homopolymer or copolymer. The comonomer is preferably a C4 toC20 linear, branched or cyclic monomer, and in one embodiment is a C4 toC12 linear or branched alpha-olefin, preferably butene, pentene, hexene,heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl-hexene-1, and the like. Ethylene may bepresent at 5 mol % or less.

[0126] In another embodiment the polymer produced herein is a copolymerof one or more linear or branched C3 to C30 prochiral alpha-olefins orC5 to C30 ring containing olefins or combinations thereof capable ofbeing polymerized by either stereospecific and non-stereospecificcatalysts. Prochiral, as used herein, refers to monomers that favor theformation of isotactic or syndiotactic polymer when polymerized usingstereospecific catalyst(s).

[0127] The polymerizable olefinic moiety can be linear, branched,cyclic-containing, or a mixture of these structures. Preferred linearalpha-olefins include C3 to C8 alpha-olefins, more preferably propylene,1-butene, 1-hexene, and 1-octene, even more preferably propylene or1-butene. Preferred branched alpha-olefins include 4-methyl-1-pentene,3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene, 5-ethyl-1-nonene.Preferred aromatic-group-containing monomers contain up to 30 carbonatoms. Suitable aromatic-group-containing monomers comprise at least onearomatic structure, preferably from one to three, more preferably aphenyl, indenyl, fluorenyl, or naphthyl moiety. Thearomatic-group-containing monomer further comprises at least onepolymerizable double bond such that after polymerization, the aromaticstructure will be pendant from the polymer backbone. The aromatic-groupcontaining monomer may further be substituted with one or morehydrocarbyl groups including but not limited to C1 to C10 alkyl groups.Additionally two adjacent substitutions may be joined to form a ringstructure. Preferred aromatic-group-containing monomers contain at leastone aromatic structure appended to a polymerizable olefinic moiety.Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,paramethyl styrene, 4-phenyl-1-butene and allyl benzene.

[0128] Non aromatic cyclic group containing monomers are also preferred.These monomers can contain up to 30 carbon atoms. Suitable non-aromaticcyclic group containing monomers preferably have at least onepolymerizable olefinic group that is either pendant on the cyclicstructure or is part of the cyclic structure. The cyclic structure mayalso be further substituted by one or more hydrocarbyl groups such as,but not limited to, C1 to C10 alkyl groups. Preferred non-aromaticcyclic group containing monomers include vinylcyclohexane,vinylcyclohexene, vinylnorbornene, ethylidene norbornene,cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantaneand the like.

[0129] Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C4 to C30, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.,di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

[0130] In a preferred embodiment one or more dienes are present in thepolymer produced herein at up to 10 weight %, preferably at 0.00001 to1.0 weight %, preferably 0.002 to 0.5 weight %, even more preferably0.003 to 0.2 weight %, based upon the total weight of the composition.In some embodiments 500 ppm or less of diene is added to thepolymerization, preferably 400 ppm or less, preferably or 300 ppm orless. In other embodiments at least 50 ppm of diene is added to thepolymerization, or 100 ppm or more, or 150 ppm or more.

[0131] In a preferred embodiment the olefin polymer ishomo-polypropylene. In another preferred embodiment the olefin polymercomprises propylene, ethylene, preferably less than 5 mol % ethylene,and at least one divinyl comonomer. In another preferred embodiment theolefin polymer comprises propylene and at least one divinyl comonomer.

[0132] In another embodiment, the olefin polymer comprises:

[0133] a first monomer present at from 40 to 95 mole %, preferably 50 to90 mole %, preferably 60 to 80 mole %, and

[0134] a comonomer present at from 5 to 40 mole %, preferably 10 to 60mole %, more preferably 20 to 40 mole %, and

[0135] a termonomer present at from 0 to 10 mole %, more preferably from0.5 to 5 mole %, more preferably 1 to 3 mole %.

[0136] In a preferred embodiment the first monomer comprises one or moreof any C3 to C8 linear, branched or cyclic alpha-olefins, includingpropylene, butene (and all isomers thereof), pentene (and all isomersthereof), hexene (and all isomers thereof), heptene (and all isomersthereof), and octene (and all isomers thereof). Preferred monomersinclude propylene, 1-butene, 1-hexene, 1-octene, and the like.

[0137] In a preferred embodiment the comonomer comprises one or more ofany C2 to C40 linear, branched or cyclic alpha-olefins (providedethylene, if present, is present at 5 mole % or less), includingethylene, propylene, butene, pentene, hexene, heptene, and octene,nonene, decene, undecene, dodecene, hexadecene, styrene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1, norborneneand cyclopentene.

[0138] In a preferred embodiment the termonomer comprises one or more ofany C2 to C40 linear, branched or cyclic alpha-olefins, (preferablyethylene, if present, is present at 5 mole % or less), including, butnot limited to, ethylene, propylene, butene, pentene, hexene, heptene,and octene, nonene, decene, undecene, dodecene, hexadecene, butadiene,1,5-hexadiene, 1,6-heptadiene, 1,4-pentadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, styrene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1, andcyclopentadiene.

[0139] In a preferred embodiment the polymer comprises propylene andfrom 0 to 50 mole % ethylene, preferably from 0 to 30 mole % ethylene,more preferably from 0 to 15 mole % ethylene, more preferably from 0 to10 mole % ethylene, more preferably from 0 to 5 mole % ethylene.

[0140] In a preferred embodiment the polymer comprises propylene andfrom 0 to 50 mole % butene, preferably from 0 to 30 mole % butene, morepreferably from 0 to 15 mole % butene, more preferably from 0 to 10 mole% butene, more preferably from 0 to 5 mole % butene.

[0141] In a preferred embodiment the polymer comprises propylene andfrom 0 to 50 mole % hexene, preferably from 0 to 30 mole % hexene, morepreferably from 0 to 15 mole % hexene, more preferably from 0 to 10 mole% hexene, more preferably from 0 to 5 mole % hexene.

[0142] Process

[0143] This invention further relates to a process to produce the olefinpolymers described above comprising:

[0144] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less and a heat of fusion of 10 J/gor less;

[0145] 2) selecting a second catalyst component capable of producingpolymer having an Mw of 100,000 or less and a crystallinity of 20% ormore;

[0146] 3) contacting the catalyst components in the presence of one ormore activators with one or more olefins, in a reaction zone.

[0147] This invention further relates to a process to produce the olefinpolymers described above comprising:

[0148] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less and a heat of fusion of 10 J/gor less;

[0149] 2) selecting a second catalyst component capable of producingpolymer having an Mw of 100,000 or less and a crystallinity of 20% ormore;

[0150] 3) contacting the catalyst components in the presence of one ormore activators with one or more olefins and one or more dienes, in areaction zone.

[0151] This invention further relates to a process to produce the olefinpolymers described above comprising:

[0152] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less and a heat of fusion of 70 J/gor less, capable of polymerizing macromonomers having reactive termini;

[0153] 2) selecting a second catalyst component capable of producingmacromonomers having reactive termini, an Mw of 100,000 or less and acrystallinity of 30% or more;

[0154] 3) contacting the catalyst components in the presence of one ormore activators with one or more olefins, and optionally a diolefin in areaction zone.

[0155] This invention further relates to a process to produce the olefinpolymers described above comprising:

[0156] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 30,000 or less and a heat of fusion of 10 J/g orless, capable of polymerizing macromonomers having reactive termini;

[0157] 2) selecting a second catalyst component capable of producingmacromonomers having reactive termini, an Mw of 30,000 or less and acrystallinity of 20% or more;

[0158] 3) contacting the catalyst components in the presence of one ormore activators with propylene, and optionally other olefins, in areaction zone

[0159] In another preferred embodiment this invention relates to acontinuous process to produce a branched olefin polymer comprising:

[0160] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less, preferably 80,000 or less,preferably 60,000 or less and a crystallinity of 5% or less, preferably3% or less, more preferably 2% or less, under selected polymerizationconditions;

[0161] 2) selecting a second catalyst component capable of producingpolymer having an Mw of 100,000 or less, preferably 80,000 or less,preferably 60,000 or less and a crystallinity of 20% or more, preferably30% or more, more preferably 40% or more at the selected polymerizationconditions;

[0162] 3) contacting, under the selected polymerization conditions, thecatalyst components in the presence of one or more activators with oneor more C3 to C40 olefins, preferably one or more C3 to C12 olefins,preferably C3 and one or more of ethylene and/or C4 to C20 comonomers,and, optionally one or more diolefins, preferably a C4 to C20 diene;

[0163] 4) at a temperature of greater than 70° C., preferably greaterthan 100° C., preferably greater than 105° C., more preferably greaterthan 110° C., more preferably greater than 115° C.;

[0164] 5) at a residence time of 120 minutes or less, preferably 60minutes or less, preferably 50 minutes or less, preferably 40 minutes,preferably 30 minutes or less, preferably 25 minutes or less, morepreferably 20 minutes or less, more preferably 15 minutes or less, morepreferably at 10 minutes or less, more preferably at 5 minutes or less,more preferably at 3 minutes or less, alternately the residence time maybe between 60 and 120 minutes;

[0165] 6) wherein the ratio of the first catalyst to the second catalystis from 1:1 to 50: 1, preferably 1:1 to 20: 1, more preferably 1:1 to1:10;

[0166] 7) wherein the activity of the catalyst components is at least 3kilograms, preferably at least 50 kilograms, more preferably at least100 kilograms, more preferably at least 200 kilograms, more preferably,300 kilograms, more preferably 400 kilograms, more preferably 500kilograms of polymer per gram of the catalyst mixture; and wherein atleast 80%, preferably at least 85%, more preferably at least 90%, morepreferably at least 95% of the olefins are converted to polymer.

[0167] In another embodiment the a first catalyst component is capableof producing a polymer having an Mw of 100,000 or less and acrystallinity of 5% or less at selected polymerization conditions andthe second catalyst component is capable of producing polymer having anMw of 100,000 or less and a crystallinity of 20% or more at the selectedpolymerization conditions.

[0168] In another embodiment at least 20% or more of the olefins areconverted to polymer, preferably 20% or more, more preferably 60% ormore, more preferably 75% or more, more preferably 85% or more, morepreferably 95% or more.

[0169] In a preferred embodiment the process described above takes placein a solution phase, slurry or bulk phase polymerization process.

[0170] By continuous is meant a system that operates (or is intended tooperate) without interruption or cessation. For example a continuousprocess to produce a polymer would be one where the reactants arecontinually introduced into one or more reactors and polymer product iscontinually withdrawn.

[0171] In another preferred embodiment, in the process described abovethe concentrations of the reactants vary by 20% or less in the reactionzone during the residence time, preferably by 15% or less, morepreferably by 10% or less. In a preferred embodiment the concentrationof the monomer(s) remains constant in the reaction zone during theresidence time. Preferably the concentration of the monomer(s) varies by20% or less, preferably by 15% or less, more preferably by 10% or less,more preferably by 5% or less.

[0172] In a preferred embodiment the concentration of the catalystcomponents remains constant in the reaction zone during the residencetime. Preferably the concentration of the monomer(s) varies by 20% orless, preferably by 15% or less, more preferably by 10% or less, morepreferably by 5% or less.

[0173] In a preferred embodiment the concentration of the activator(s)remains constant in the reaction zone during the residence time.Preferably the concentration of the monomer(s) varies by 20% or less,preferably by 15% or less, more preferably by 10% or less, morepreferably by 5% or less.

[0174] In another preferred embodiment a third catalyst (or more) may bepresent in the processes described above. The third catalyst may be anyof the catalyst components listed herein. Preferred third catalystsinclude catalysts that are capable of producing waxes. Other preferredthird catalysts may include any catalyst described herein. One mayselect two or more catalysts to produce various macromonomers havingreactive termini, used in combination with a catalyst that canpolymerize such macromonomers. One may select two or more catalysts thatcan polymerize macromonomers and one catalyst that can producemacromonomers with reactive termini. Likewise one could also selectthree catalysts that produce different polymers under the same reactionconditions. For example one could select a catalyst that produces asomewhat crystalline polymer, one that produces a very crystallinepolymer and one that produces an amorphous polymer, any of which mayproduce macromonomers with reactive termini or polymerize polymershaving reactive termini. Similarly one could select two catalysts, onethat produces crystalline polymers and one that produces an amorphouspolymer, any of which may make macromonomers with reactive termini orpolymerize polymers having reactive termini. Likewise one could select acatalyst that produces a somewhat crystalline polymer, one that producesa wax and one that produces an amorphous polymer, any of which may makemacromonomers with reactive termini or polymerize polymers havingreactive termini.

[0175] By reaction zone is meant an area where the activated catalystand monomers can react.

[0176] By macromonomers having reactive termini is meant a polymerhaving twelve or more carbon atoms (preferably 20 or more, morepreferably 30 or more, more preferably between 12 and 8000 carbon atoms)and having a vinyl, vinylidene, vinylene or other terminal group thatcan be polymerized into a growing polymer chain. By capable ofpolymerizing macromonomer having reactive termini is meant a catalystcomponent that can incorporate a macromonomer (which tend to bemolecules larger than a typical single monomer such as ethylene orpropylene), having reactive termini into a growing polymer chain. Vinylterminated chains are generally more reactive than vinylene orvinylidene terminated chains.

[0177] In a particular embodiment the present invention is directed to apolyolefin polymer produced by copolymerizing one or more C₃ or higheralpha-olefins and/or one or more di-vinyl monomers, and optionally up to5 mol % ethylene, in the presence of at least one stereospecificcatalyst system and at least one other catalyst system in the samepolymerization medium. Preferably, the polymerizations are carried outsimultaneously in the presence of both catalysts. The polymer soproduced may contain amorphous polymer segments and crystalline polymersegments in which at least some of the segments are linked. Typicallythe amorphous and the crystalline polymer segments are copolymers of oneor more alpha-olefins (optionally including up to 5 mol % ethylene)and/or one or more monomers having at least two olefinically unsaturatedbonds. Both of these unsaturated bonds are suitable for and readilyincorporated into a growing polymer chain by coordination polymerizationusing either the first or second catalyst systems independently suchthat the di-olefin is incorporated into polymer segments produced byboth catalysts in the mixed catalyst system according to this invention.In a preferred embodiment these monomers having at least twoolefinically unsaturated bonds are di-olefins, preferably di-vinylmonomers. Crosslinking of at least a portion of the mixture of polymersegments is believed to be accomplished during the polymerization of thecomposition by incorporation of a portion of di-vinyl comonomers intotwo polymer segments, thus producing a crosslink between those segments.

[0178] In another embodiment, polyolefin branch-block compositionscontaining amorphous and semi-crystalline components may be prepared ina single reactor to yield desired property balance. In particular,aPP-g-scPP branch structures may be produced in-situ in a continuoussolution reactor using mixed catalysts and propylene as the preferredfeed. In one embodiment stereospecific bridged bis-indenyl group 4catalysts can be selected to produce semicrystalline PP macromonomers.(All references to the Periodic Table of the Elements are to the Tablepublished in Chemical and Engineering News, 63(5), 27, 1985.) A bridgedmono-cyclopentadienyl heteroatom group 4 catalyst can be used to buildamorphous PP (aPP) backbone while simultaneously incorporating some ofthe semi-crystalline macromonomers (scPP). This is believed to produce aaPP-g-scPP structure where the “-g-” indicates that the polymer typesare at least partially grafted. By selecting the catalysts, thepolymerization reaction conditions, and/or by introducing a dienemodifier, the amorphous and crystalline components can be linkedtogether to produce various branch-block structures. To effectivelyincorporate into a growing chain, a macromonomer with vinyl end group ispreferred. Other types of chain end unsaturations (vinylene andvinylidene) can also be used. While not wishing to be bound by theory,branch-block copolymer is believed to comprise an amorphous backbonehaving crystalline side chains originating from the scPP macromonomersand the sidechains are believed to be polypropylene macromonomers, whichcan be prepared under solution polymerization conditions with catalystssuitable for preparing either of isotactic or syndiotacticpolypropylene.

[0179] A preferred reaction process to produce polypropylenemacromonomers having high levels of terminal vinyl unsaturation isdescribed in U.S. Pat. No. 6,117,962. Typically used catalysts arestereorigid, chiral or asymmetric, bridged metallocenes. See, forexample, U.S. Pat. No. 4,892,851, U.S. Pat. No. 5,017,714, U.S. Pat. No.5,132,281, U.S. Pat. No. 5,296,434, U.S. Pat. No. 5,278,264, U.S. Pat.No. 5,304,614, U.S. Pat. No. 5,510,502, WO-A-(PCT/US92/10066)WO-A-93/19103, EP-A2-0 577 581, EP-A1-0 578 838, and academic literature“The Influence of Aromatic Substituents on the Polymerization Behaviorof Bridged Zirconocene Catalysts”, Spaleck, W., et al., Organometallics1994, 13, 954-963, and “ansa-Zirconocene Polymerization Catalysts withAnnelated Ring Ligands-Effects on Catalytic Activity and Polymer ChainLengths”, Brinzinger, H., et al, Organometallics 1994, 13, 964-970, anddocuments referred to therein.

[0180] In some embodiments, the first catalyst which comprises astereorigid transition metal pre-catalyst compound used to produce thesemi-crystalline polypropylene macromonomers of the present invention isselected from the group consisting of racemic bridgedbis(indenyl)zirconocenes or hafnocenes. In a another embodiment, thetransition metal pre-catalyst compound is a rac-dimethylsilyl-bridgedbis(indenyl)zirconocene or hafnocene. In another embodiment, thetransition metal pre-catalyst compound is rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium or hafnium dichloride ordimethyl. In another preferred embodiment, the transition metal catalystis a rac-dimethylsilyl-bridged bis(indenyl)hafnocene such asrac-dimethylsilyl bis(indenyl)hafnium dimethyl or dichloride.

[0181] It is believed that the fraction of branch-block and the level ofbranching depend on the availability of macromonomers with unsaturatedchain end and macromonomer incorporation capability of the specificcatalyst. To increase the population of aPP-g-scPP branch-blockcomposition, one typically operates within a process window that favorsmacromonomer production and insertion. Such conditions have beendescribed in U.S. Pat. No. 6,117,962 and the journal article by W. Wenget al., Macromol. Rapid Commun., 2000, 21, 1103-1107 and are furtherillustrated by the examples therein.

[0182] It is also believed that the higher the population of vinylterminated scPP macromonomers the higher the probability of getting themincorporated into aPP backbone and therefore the higher the branch-blockpopulation.

[0183] To further increase the population of macromonomers having vinylchain ends diolefin monomers can be introduced into the reaction medium.The resultant product is typically a blend comprised of isotacticpolypropylene segments, atactic polypropylene segments, and increasedpopulation of branch-block species resulting from the additionalcouplings brought about by the diolefin crosslinking agent.

[0184] Crosslinking typically refers to the connection of two polymersegments by incorporation of each double bond of a diolefin monomer intotwo different polymer segments. The polymer segments so connected can bethe same or different, with respect to their crystallinity. Three ormore polymer segments may also be connected via incorporation of two ormore diolefins in on polymer segment into two other polymer segments.

[0185] A consideration for selection of the monomer, or combinations ofmonomers, is that, both crystalline and amorphous polymer segments canbe formed with the selection of two or more different catalyst systems.In some embodiments it is further desired that the level ofincorporation of the diolefin monomer, if present, into the crystallinesegments be limited to an amount that will not substantially alter itscrystallinity. The diolefin coupling agent is typically kept minimum toinsure the overall composition has a viscosity of 8000 mPa·s or less forsome adhesive applications.

[0186] As mentioned above, to increase the population of aPP-g-scPPbranch-block composition, one typically operates within a process windowthat favors macromonomer production and insertion. Favorable conditionsinclude:

[0187] 1) High concentration of catalyst producing the semi-crystallinevinyl terminated macromonomers, and or

[0188] 2) Adjusting the Al/metal ratio; and or

[0189] 3) High operating temperature; and or

[0190] 4) Catalyst structure that has a high affinity for macromonomerincorporation; and or

[0191] 5) Relatively long residence time; and or

[0192] 6) High monomer conversion (monomer starvation condition enhancesthe insertion of macromonomer); and or

[0193] 7) Addition of modifier (diene) to enhance the population ofvinyl terminated macromonomers.

[0194] Another method of enhancing aPP-g-scPP branch block compositionsis to add in a chain transfer agent that transfers a vinyl group to theend of the polymer chain while deactivating the catalyst. Such chaintransfer agents include, but are not limited to, vinyl chloride, vinylfluoride, vinyl bromide. In the process, the catalyst is reactivated bythe presence of an aluminum alkyl activator such as an alumoxane(typically methylalumoxane).

[0195] Similarly, melting and crystallization characteristics can becontrolled through catalyst selection, comonomer addition and changes inprocess conditions such as temperature and catalyst ratio if more thanone catalyst is used.

[0196] Catalyst Compounds

[0197] Any catalyst compound that can produce the desired polymerspecies may be used in the practice of this invention. In thedescription herein the transition metal compound may be described as acatalyst precursor, a pre-catalyst compound or a catalyst compound, andthese terms are used interchangeably. A catalyst system is combinationof a catalyst precursor and an activator.

[0198] Catalyst Compounds and Selection

[0199] Any pre-catalyst compound (catalyst precursor compound) that canproduce the desired polymer species may be used in the practice of thisinvention. Pre-catalyst compounds which may be utilized in the processof the invention include metallocene transition metal compounds(containing one, two, or three cyclopentadienyl ligands per metal atom),non-metallocene early transition metal compounds (including those withamide and/or phenoxide type ligands), non-metallocene late transitionmetal compounds (including those with diimine or diiminepyridylligands), and other transition metal compounds.

[0200] Generally, bulky ligand metallocene compounds (pre-catalysts)useful in this invention include half and full sandwich compounds havingone or more bulky ligands bonded to at least one metal atom. Typicalbulky ligand metallocene compounds are generally described as containingone or more bulky ligand(s) and one or more leaving group(s) bonded toat least one metal atom. The bulky ligands are generally represented byone or more open, acyclic, or fused ring(s) or ring system(s) or acombination thereof. These bulky ligands, preferably the ring(s) or ringsystem(s) are typically composed of atoms selected from Groups 13 to 16atoms of the Periodic Table of Elements, preferably the atoms areselected from the group consisting of carbon, nitrogen, oxygen, silicon,sulfur, phosphorous, germanium, boron and aluminum or a combinationthereof. Most preferably, the ring(s) or ring system(s) are composed ofcarbon atoms such as but not limited to those cyclopentadienyl ligandsor cyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadienyl, a cyclooctatetraendiyl, acyclobutadienyl, or a substituted allyl ligand. Other ligands that canfunction similarly to a cyclopentadienyl-type ligand include amides,phosphides, imines, phosphinimines, amidinates, and ortho-substitutedphenoxides. The metal atom is preferably selected from Groups 3 through15 and or lanthanide or actinide series of the Periodic Table ofElements. Preferably the metal is a transition metal from Groups 3through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

[0201] In one embodiment, the catalyst composition useful in theinvention includes one or more bulky ligand metallocene catalystcompounds represented by the formula:

L^(A)L^(B)MQ*_(n)  (1)

[0202] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthanide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is a Group 4 transition metal,even more preferably M is zirconium, hafnium or titanium. The bulkyligands, L^(A) and L^(B), are open, acyclic or fused ring(s) or ringsystem(s) and are any ancillary ligand system, including unsubstitutedor substituted, cyclopentadienyl ligands or cyclopentadienyl-typeligands, heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,dibenzo[b,h]fluorenyl ligands, benzo[b]fluorenyl ligands,cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenylligands, azulene ligands, pentalene ligands, phosphoyl ligands,phosphinimine (WO 99/40125), pyrrolyl ligands, pyrozolyl ligands,carbazolyl ligands, boratobenzene ligands and the like, includinghydrogenated versions thereof, for example tetrahydroindenyl ligands. Inone embodiment, L^(A) and L^(B) may be any other ligand structurecapable of π-bonding to M. In yet another embodiment, the atomicmolecular weight (MW) of L^(A) or L^(B) exceeds 60 a.m.u., preferablygreater than 65 a.m.u. In another embodiment, L^(A) and L^(B) maycomprise one or more heteroatoms, for example, nitrogen, silicon, boron,germanium, sulfur and phosphorous, in combination with carbon atoms toform an open, acyclic, or preferably a fused, ring or ring system, forexample, a hetero-cyclopentadienyl ancillary ligand. Other L^(A) andL^(B) bulky ligands include but are not limited to bulky amides,phosphides, alkoxides, aryloxides, imides, carbolides, borollides,porphyrins, phthalocyanines, corrins and other polyazomacrocycles.Independently, each L^(A) and L^(B) may be the same or different type ofbulky ligand that is bonded to M. In one embodiment of Formula 1 onlyone of either L^(A) or L^(B) is present.

[0203] Independently, each L^(A) and L^(B) may be unsubstituted orsubstituted with a combination of substituent groups R*. Non-limitingexamples of substituent groups R* include one or more from the groupselected from hydrogen, or linear or branched alkyl radicals, alkenylradicals, alkynyl radicals, cycloalkyl radicals, aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals or combination thereof. In a preferred embodiment,substituent groups R* have up to 50 non-hydrogen atoms, preferably from1 to 30 carbon, that can also be substituted with halogens orheteroatoms or the like. Non-limiting examples of alkyl substituents R*include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl,cyclohexyl, benzyl or phenyl groups and the like, including all theirisomers, for example tertiary butyl, isopropyl, and the like. Otherhydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl,iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substitutedorganometalloid radicals including trimethylsilyl, trimethylgermyl,methyldiethylsilyl and the like; and halocarbyl-substitutedorganometalloid radicals including tris(trifluoromethyl)silyl,methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like;and disubstituted boron radicals including dimethylboron for example;and disubstituted pnictogen radicals including dimethylamine,dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogenradicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide andethylsulfide. Non-hydrogen substituents R* include the atoms carbon,silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur,germanium and the like, including olefins such as but not limited toolefinically unsaturated substituents including vinyl-terminatedligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like.Also, at least two R* groups, preferably two adjacent R groups, arejoined to form a ring structure having from 3 to 30 atoms selected fromcarbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum,boron or a combination thereof. Also, a substituent group, R*, may alsobe a diradical bonded to L at one end and forming a carbon sigma bond tothe metal M. Other ligands may be bonded to the metal M, such as atleast one leaving group Q*. In one embodiment, Q* is a monoanioniclabile ligand having a sigma-bond to M. Depending on the oxidation stateof the metal, the value for n is 0, 1 or 2 such that Formula 1 aboverepresents a neutral bulky ligand metallocene catalyst compound.Non-limiting examples of Q* ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q*'s form a partof a fused ring or ring system. Other examples of Q* ligands includethose substituents for R* as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene (both Q*),pentamethylene (both Q*), methylidene (both Q*), methoxy, ethoxy,propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphideradicals and the like.

[0204] In another embodiment, the catalyst composition useful in theinvention may include one or more bulky ligand metallocene catalystcompounds where L^(A) and L^(B) of Formula 1 are bridged to each otherby at least one bridging group, A*, as represented by Formula 2.

L^(A)A*L^(B)MQ*_(n)  (2)

[0205] The compounds of Formula 2 are known as bridged, bulky ligandmetallocene catalyst compounds. L^(A), L^(B), M, Q* and n are as definedabove. Non-limiting examples of bridging group A* include bridginggroups containing at least one Group 13 to 16 atom, often referred to asa divalent moiety such as but not limited to at least one of a carbon,oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or acombination thereof. Preferably bridging group A* contains a carbon,silicon or germanium atom, most preferably A* contains at least onesilicon atom or at least one carbon atom. The bridging group A* may alsocontain substituent groups R* as defined above including halogens andiron. Non-limiting examples of bridging group A* may be represented byR′₂C, R′₂CCR′₂, R′₂Si, R′₂SiCR′₂, R′₂SiSiR′₂ R′₂Ge, R′P, R′N, R′B whereR′ is independently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene catalyst compounds of Formula 2 have two or more bridginggroups A* (EP 664 301 B1). In another embodiment, the bulky ligandmetallocene catalyst compounds are those where the R* substituents onthe bulky ligands L^(A) and L^(B) of Formulas 1 and 2 are substitutedwith the same or different number of substituents on each of the bulkyligands. In another embodiment, the bulky ligands L^(A) and L^(B) ofFormulas 1 and 2 are different from each other.

[0206] Other bulky ligand metallocene catalyst compounds and catalystsystems useful in the invention may include those described in U.S. Pat.Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517 and5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fullyincorporated by reference.

[0207] In another embodiment, the catalyst compositions useful in theinvention may include bridged heteroatom, mono-bulky ligand metallocenecompounds. These types of catalysts and catalyst systems are describedin, for example, PCT publication WO 92/00333, WO 94/07928, WO 91/04257,WO 94/03506, WO96/00244, WO 97/15602 and WO 99/20637 and U.S. Pat. Nos.5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 andEuropean publication EP-A-0 420 436, all of which are herein fullyincorporated by reference.

[0208] In another embodiment, the catalyst composition useful in theinvention includes one or more bulky ligand metallocene catalystcompounds represented by Formula 3:

L^(C)A*J*MQ*_(n)  (3)

[0209] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthanides of the Periodic Table ofElements, preferably M is a Group 3 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, and isespecially titanium; L^(C) is a substituted or unsubstituted bulkyligand bonded to M; J* is bonded to M; A* is bonded to J* and L^(C); J*is a heteroatom ancillary ligand; and A* is a bridging group; Q* is aunivalent anionic ligand; and n is the integer 0, 1 or 2. In Formula 3above, L^(C), A* and J* form a fused ring system. In an embodiment, Lcof Formula 3 is as defined above for LA. A*, M and Q* of Formula 3 areas defined above in Formula 1. In Formula 3, J* is a heteroatomcontaining ligand in which J* is an element with a coordination numberof three from Group 15 or an element with a coordination number of twofrom Group 16 of the Periodic Table of Elements. Preferably J* containsa nitrogen, phosphorus, oxygen or sulfur atom with nitrogen being mostpreferred. In an embodiment of the invention, the bulky ligandmetallocene catalyst compounds are heterocyclic ligand complexes wherethe bulky ligands, the ring(s) or ring system(s), include one or moreheteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene catalyst compounds are described in WO96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005and U.S. Pat. Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611,5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporatedby reference.

[0210] In one embodiment, the bulky ligand metallocene compounds(pre-catalysts) are those complexes based on bidentate ligandscontaining pyridine or quinoline moieties, such as those described inU.S. application Ser. No. 09/103,620 filed Jun. 23, 1998, which isherein incorporated by reference. In another embodiment, the bulkyligand metallocene catalyst compounds are those described in PCTpublications WO 99/01481 and WO 98/42664, which are fully incorporatedherein by reference.

[0211] In another embodiment, the bulky ligand metallocene catalystcompound is a complex of a metal, preferably a transition metal, a bulkyligand, preferably a substituted or unsubstituted pi-bonded ligand, andone or more heteroallyl moieties, such as those described in U.S. Pat.Nos. 5,527,752 and 5,747,406 and EP-B 1-0 735 057, all of which areherein fully incorporated by reference.

[0212] In another embodiment, the bulky ligand metallocene catalystcompounds are those described in PCT publications WO 99/01481 and WO98/42664, which are fully incorporated herein by reference.

[0213] Useful Group 6 bulky ligand metallocene catalyst Systems aredescribed in U.S. Pat. No. 5,942,462, which is incorporated herein byreference.

[0214] Still other useful catalysts include those multinuclearmetallocene catalysts as described in WO 99/20665 and 6,010,794, andtransition metal metaaracyle structures described in EP 0 969 101 A2,which are herein incorporated herein by reference. Other metallocenecatalysts include those described in EP 0 950 667 A1, doublecross-linked metallocene catalysts (EP 0 970 074 A1), tetheredmetallocenes (EP 970 963 A2) and those sulfonyl catalysts described inU.S. Pat. No. 6,008,394, which are incorporated herein by reference.

[0215] It is also contemplated that in one embodiment the bulky ligandmetallocene catalysts, described above, include their structural oroptical or enantiomeric isomers (meso and racemic isomers, for examplesee U.S. Pat. No. 5,852,143, incorporated herein by reference) andmixtures thereof.

[0216] It is further contemplated that any one of the bulky ligandmetallocene catalyst compounds, described above, have at least onefluoride or fluorine containing leaving group as described in U.S.application Ser. No. 09/191,916 filed Nov. 13, 1998.

[0217] The Group 15 containing metal compounds utilized in the catalystcomposition of the invention are prepared by methods known in the art,such as those disclosed in EP 0 893 454 A1, U.S. Pat. No. 5,889,128 andthe references cited in U.S. Pat. No. 5,889,128 which are all hereinincorporated by reference. U.S. application Ser. No. 09/312,878, filedMay 17, 1999, discloses a gas or slurry phase polymerization processusing a supported bisamide catalyst, which is also incorporated hereinby reference.

[0218] For additional information of Group 15 containing metalcompounds, please see Mitsui Chemicals, Inc. in EP 0 893 454 A1 whichdiscloses transition metal amides combined with activators to polymerizeolefins.

[0219] In one embodiment the Group 15 containing metal compound isallowed to age prior to use as a polymerization. It has been noted on atleast one occasion that one such catalyst compound (aged at least 48hours) performed better than a newly prepared catalyst compound.

[0220] It is further contemplated that bis-amide based pre-catalysts maybe used. Exemplary compounds include those described in the patentliterature. International patent publications WO 96/23010, WO 97/48735and Gibson, et al., Chem. Comm., pp. 849-850 (1998), which disclosediimine-based ligands for Group-8-10 compounds that undergo ionicactivation and polymerize olefins. Polymerization catalyst systems fromGroup-5-10 metals, in which the active center is highly oxidized andstabilized by low-coordination-number, polyanionic, ligand systems, aredescribed in U.S. Pat. No. 5,502,124 and its divisional U.S. Pat. No.5,504,049. See also the Group-5 organometallic catalyst compounds ofU.S. Pat. No. 5,851,945 and the tridentate-ligand-containing,Group-5-10, organometallic catalysts of U.S. Pat. No. 6,294,495.Group-11 catalyst precursor compounds, activatable with ionizingcocatalysts, useful for olefin and vinylic polar molecules are describedin WO 99/30822.

[0221] Other useful catalyst compounds are those Group 5 and 6 metalimido complexes described in EP-A2-0 816 384 and U.S. Pat. No.5,851,945, which is incorporated herein by reference. In addition,metallocene catalysts include bridged bis(arylamido) Group 4 compoundsdescribed by D. H. McConville, et al., in Organometallics 1995, 14,5478-5480, which is herein incorporated by reference. In addition,bridged bis(amido) catalyst compounds are described in WO 96/27439,which is herein incorporated by reference. Other useful catalysts aredescribed as bis(hydroxy aromatic nitrogen ligands) in U.S. Pat. No.5,852,146, which is incorporated herein by reference. Other usefulcatalysts containing one or more Group 15 atoms include those describedin WO 98/46651, which is herein incorporated herein by reference.

[0222] U.S. Pat. No. 5,318,935 describes bridged and unbridged, bisamidocatalyst compounds of Group-4 metals capable of alpha-olefinspolymerization. Bridged bi(arylamido)-Group-4 compounds for olefinpolymerization are described by D. H. McConville, et al., inOrganometallics 1995, 14, 5478-5480. This reference presents syntheticmethods and compound characterizations. Further work appearing in D. H.McConville, et al, Macromolecules 1996, 29, 5241-5243, describes bridgedbis(arylamido)-Group-4 compounds that are polymerization catalysts for1-hexene. Additional invention-suitable transition metal compoundsinclude those described in WO 96/40805. Cationic Group-3- orLanthanide-metal olefin polymerization complexes are disclosed incopending U.S. application Ser. No. 09/408,050, filed 29 Sep. 1999. Amonoanionic bidentate ligand and two monoanionic ligands stabilize thosecatalyst precursors, which can be activated with this invention's ioniccocatalysts.

[0223] The literature describes many additional suitablecatalyst-precursor compounds. Compounds that contain abstractableligands or that can be alkylated to contain abstractable ligands suitthis invention. See, for instance, V. C. Gibson, et al; “The Search forNew-Generation Olefin Polymerization Catalysts: Life BeyondMetallocenes”, Angew. Chem. Int. Ed., 38, 428-447 (1999).

[0224] This invention may also be practiced with the catalystscontaining phenoxide ligands such as those disclosed in EP 0 874 005 A1,which in incorporated by reference herein.

[0225] In another embodiment, conventional-type transition metalcatalysts may be used in the practice of this invention.Conventional-type transition metal catalysts are those traditionalZiegler-Natta, vanadium and Phillips-type catalysts well known in theart. Such as, for example Ziegler-Natta catalysts as described inZiegler-Natta Catalysts and Polymerizations, John Boor, Academic Press,New York, 1979. Examples of conventional-type transition metal catalystsare also discussed in U.S. Pat. Nos. 4,115,639, 4,077,904, 4,482,687,4,564,605, 4,721,763, 4,879,359 and 4,960,741, all of which are hereinfully incorporated by reference. The conventional-type transition metalcatalyst compounds that may be used in the present invention includetransition metal compounds from Groups 3 to 17, preferably 4 to 12, morepreferably 4 to 6 of the Periodic Table of Elements.

[0226] Preferred conventional-type transition metal catalysts may berepresented by the formula: MR_(x), where M is a metal from Groups 3 to17, preferably Group 4 to 6, more preferably Group 4, most preferablytitanium; R is a halogen or a hydrocarbyloxy group; and x is theoxidation state of the metal M. Non-limiting examples of R includealkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examplesof conventional-type transition metal catalysts where M is titaniuminclude TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl,Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂, TiCl₃·1/3AlCl₃ and Ti(OC₁₂H₂₅)Cl₃.

[0227] Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred.

[0228] British Patent Application 2,105,355 and U.S. Pat. No. 5,317,036,herein incorporated by reference, describes various conventional-typevanadium catalyst compounds. Non-limiting examples of conventional-typevanadium catalyst compounds include vanadyl trihalide, alkoxy halidesand alkoxides such as VOCl₃, VOCl₂(OBu) where Bu=butyl and VO(OC₂H₅)₃;vanadium tetra-halide and vanadium alkoxy halides such as VCl₄ andVCl₃(OBu); vanadium and vanadyl acetyl acetonates and chloroacetylacetonates such as V(AcAc)₃ and VOCl₂(AcAc) where (AcAc) is an acetylacetonate. The preferred conventional-type vanadium catalyst compoundsare VOCl₃, VCl₄ and VOCl₂—OR where R is a hydrocarbon radical,preferably a C₁ to C₁₀ aliphatic or aromatic hydrocarbon radical such asethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl,tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

[0229] Conventional-type chromium catalyst compounds, often referred toas Phillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which areherein fully incorporated by reference.

[0230] Still other conventional-type transition metal catalyst compoundsand catalyst systems suitable for use in the present invention aredisclosed in U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062,4,379,758, 5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164 and5,869,585 and published EP-A2 0 416 815 A2 and EP-A1 0 420 436, whichare all herein incorporated by reference.

[0231] Other catalysts may include cationic catalysts such as AlCl₃, andother cobalt, iron, nickel and palladium catalysts well known in theart. See for example U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and4,689,437, all of which are incorporated herein by reference.

[0232] It is also contemplated that other catalysts can be combined withthe catalyst compounds in the catalyst composition useful in theinvention. For example, see U.S. Pat. Nos. 4,937,299, 4,935,474,5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of which are hereinfully incorporated herein reference.

[0233] It is further contemplated that one or more of the catalystcompounds described above or catalyst systems may be used in combinationwith one or more conventional catalyst compounds or catalyst systems.Non-limiting examples of mixed catalysts and catalyst systems aredescribed in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418,5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and5,767,031 and PCT Publication WO 96/23010 published Aug. 1, 1996, all ofwhich are herein fully incorporated by reference.

[0234] Preferred metallocene catalysts used in this invention can morespecifically be represented by one of the following general formulae(all references to Groups being the new Group notation of the PeriodTable of the Elements as described by Chemical and Engineering News,63(5), 27, 1985):

[{[(A-Cp)MX₁]⁺}_(d)]{[B′]^(d−)}  (4)

[{[(A-Cp)MX₁L]⁺}_(d)]{[B′]^(d−)}  (5)

[0235] wherein: (A-Cp) is either (Cp), (Cp*) or Cp-A′-Cp*; Cp and Cp*are the same or different cyclopentadienyl rings substituted with fromzero to five substituent groups S″, each substituent group S″ being,independently, a radical group which is a hydrocarbyl,substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen or halogen radicals, or Cp and Cp* arecyclopentadienyl rings in which any two adjacent S″ groups are joinedforming a C₄ to C₂₀ ring to give a saturated or unsaturated polycycliccyclopentadienyl ligand; Cp and Cp* may also have one or two carbonatoms within the ring replaced by a Group 15 or 16 element especially,S, O, N or P;

[0236] A′ is a bridging group;

[0237] (C₅H_(5-y-x)S″_(x)) is a cyclopentadienyl ring substituted withfrom zero to five S″ radicals as defined above;

[0238] x is from 0 to 5 denoting the degree of substitution;

[0239] M is titanium, zirconium or hafnium;

[0240] X₁ is a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical orhalocarbyl-substituted organometalloid radical which radical mayoptionally be covalently bonded to both or either M and L or L′ or allor any M, S″ or S′, and provided that X₁ is not a substituted orunsubstituted cyclopentadienyl ring;

[0241] (JS′_(z-1-y)) is a heteroatom ligand in which J is an elementfrom Group 15 of the Periodic Table of Elements with a coordinationnumber of 3 or an element from Group 16 with a coordination number of 2;S′ is a radical group which is a hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, hydrocarbyl-substitutedorganometalloid, or halocarbyl-substituted organometalloid; and z is thecoordination number of the element J;

[0242] y is 0 or 1;

[0243] L is an olefin, diolefin or aryne ligand. L′ is the same as L,and can additionally be an amine, phosphine, ether, or sulfide ligand,or any other neutral Lewis base; L′ can also be a second transitionmetal compound of the same type such that the two metal center M and M*are bridged by X₁ and X′₁, wherein M* has the same meaning as M, X′₁, X₂and X′₂ have the same meaning as X₁, where such dimeric compounds whichare precursors to the cationic portion of the catalyst are representedby the formula:

[0244] wherein

[0245] w is an integer from 0 to 3;

[0246] B′ is a chemically stable, non-nucleophilic anionic complexhaving a molecular diameter about or greater than 4 Angstroms or ananionic Lewis-acid activator resulting from the reaction of a Lewis-acidactivator with the precursor to the cationic portion of the catalystsystem described in formulae 1-4. When B′ is a Lewis-acid activator, X₁can also be an alkyl group donated by the Lewis-acid activator; and

[0247] d is an integer representing the charge of B′.

[0248] The catalysts are preferably prepared by combining at least twocomponents. In one preferred method, the first component is acyclopentadienyl derivative of a Group 4 metal compound containing atleast one ligand which will combine with the second component or atleast a portion thereof such as a cation portion thereof. The secondcomponent is an ion-exchange compound comprising a cation which willirreversibly react with at least one ligand contained in said Group 4metal compound (first component) and a non-coordinating anion which iseither a single coordination complex comprising a plurality oflipophilic radicals covalently coordinated to and shielding a centralformally charge-bearing metal or metalloid atom or an anion comprising aplurality of boron atoms such as polyhedral boranes, carboranes andmetallacarboranes.

[0249] In general, suitable anions for the second component may be anystable and bulky anionic complex having the following molecularattributes: 1) the anion should have a molecular diameter greater than 4Angstroms; 2) the anion should form stable ammonium salts; 3) thenegative charge on the anion should be delocalized over the framework ofthe anion or be localized within the core of the anion; 4) the anionshould be a relatively poor nucleophile; and 5) the anion should not bea powerful reducing or oxidizing agent. Anions meeting thesecriteria—such as polynuclear boranes, carboranes, metallacarboranes,polyoxoanions and anionic coordination complexes are well described inthe chemical literature.

[0250] The cation portion of the second component may comprise Bronstedacids such as protons or protonated Lewis bases or may comprise Lewisacids such as ferricinum, tropylium, triphenylcarbenium or silvercations.

[0251] In another preferred method, the second component is a Lewis-acidcomplex which will react with at least one ligand of the firstcomponent, thereby forming an ionic species described in formulae 4-6with the ligand abstracted from the first component now bound to thesecond component. Alumoxanes and especially methylalumoxane, the productformed from the reaction of trimethylaluminum in an aliphatic oraromatic hydrocarbon with stoichiometric quantities of water, areparticularly preferred Lewis-acid second components. Modified alumoxanesare also preferred. Alumoxanes are well known in the art and methods fortheir preparation are illustrated by U.S. Pat. Nos. 4,542,199;4,544,762; 5,015,749; and 5,041,585. A technique for preparing modifiedalumoxanes has been disclosed in U.S. Pat. No. 5,041,584, in EPA 0 516476, and in EPA 0 561 476, which are incorporated by reference herein.

[0252] Upon combination of the first and second components, the secondcomponent reacts with one of the ligands of the first component, therebygenerating an anion pair consisting of a Group 4 metal cation and theaforementioned anion, which anion is compatible with andnon-coordinating towards the Group 4 metal cation formed from the firstcomponent. The anion of the second compound must be capable ofstabilizing the Group 4 metal cation's ability to function as a catalystand must be sufficiently labile to permit displacement by an olefin,diolefin or an acetylenically unsaturated monomer during polymerization.The catalysts of this invention may be supported. U.S. Pat. No.4,808,561, issued Feb. 28, 1989; U.S. Pat. No. 4,897,455 issued Jan. 3,1990; U.S. Pat. No. 5,057,475 issued Oct. 15, 1991; U.S. patentapplication Ser. No. 459,921 (published as PCT International publicationWO 91/09882), Canadian Patent 1,268,753, U.S. Pat. No. 5,240,894 and WO94 03506 disclose such supported catalysts and the methods to producesuch and are herein incorporated by reference.

[0253] The Group 4 metal compounds; i.e., titanium, zirconium andhafnium metallocene compounds, useful as first compounds (pre-catalysts)in the preparation of the preferred metallocene catalysts of thisinvention are cyclopentadienyl derivatives of titanium, zirconium andhafnium. In general, useful titanocenes, zirconocenes and hafnocenes maybe represented by the following general formulae:

(A-Cp)MX₁X₂  (8)

(A-Cp)ML  (9)

[0254] wherein:

[0255] (A-Cp) is either (Cp)(Cp*) or Cp-A′-Cp*; Cp and Cp* are the sameor different cyclopentadienyl rings substituted with from zero to fivesubstituent groups S″, each substituent group S″ being, independently, aradical group which is a hydrocarbyl, substituted-hydrocarbyl,halocarbyl, substituted-halocarbyl, hydrocarbyl-substitutedorganometalloid, halocarbyl-substituted organometalloid, disubstitutedboron, disubstituted pnictogen, substituted chalcogen or halogenradicals, or Cp and Cp* are cyclopentadienyl rings in which any twoadjacent S″ groups are joined forming a C₄ to C₂₀ ring to give asaturated or unsaturated polycyclic cyclopentadienyl ligand;

[0256] A′ is a bridging group;

[0257] y is 0 or 1;

[0258] (C₅H_(5-y-x)S″^(x)) is a cyclopentadienyl ring substituted withfrom zero to five S″ radicals as defined above;

[0259] x is from 0 to 5 denoting the degree of substitution;

[0260] (JS′_(z-1-y)) is a heteroatom ligand in which J is an elementfrom Group 15 of the Periodic Table of Elements with a coordinationnumber of 3 or an element from Group 16 with a coordination number of 2,S′ is a radical group which is a hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, hydrocarbyl-substitutedorganometalloid, or halocarbyl-substituted organometalloid; and z is thecoordination number of the element J;

[0261] L is an olefin, diolefin or aryne ligand. L′ is the same as L andcan additionally be an amine, phosphine, ether, or sulfide ligand, orany other neutral Lewis base; L′ can also be a second transition metalcompound of the same type such that the two metal centers M and M* arebridged by X₁ and X′₁, wherein M* has the same meaning as M, X′₁, hasthe same meaning as X₁ and X′₂ has the same meaning as X₂ where suchdimeric compounds which are precursors to the cationic portion of thecatalyst are represented by formula 7 above;

[0262] w is an integer from 0 to 3; and

[0263] X₁ and X₂ are, independently, hydride radicals, hydrocarbylradicals, substituted hydrocarbyl radicals, halocarbyl radicals,substituted halocarbyl radicals, and hydrocarbyl- andhalocarbyl-substituted organometalloid radicals, substituted pnictogenradicals, or substituted chalcogen radicals; or X₁ and X₂ are joined andbound to the metal atom to form a metallacycle ring containing fromabout 3 to about 20 carbon atoms; or X₁ and X₂ together can be anolefin, diolefin or aryne ligand; or when Lewis-acid activators, such asmethylalumoxane, which are capable of donating an X, ligand as describedabove to the transition metal component are used, X₁ and X₂ mayindependently be a halogen, alkoxide, aryloxide, amide, phosphide orother univalent anionic ligand or both X₁ and X₂ can also be joined toform a anionic chelating ligand and with the proviso that X₁ and X₂ arenot a substituted or unsubstituted cyclopentadienyl ring.

[0264] Table A depicts representative constituent moieties for themetallocene components of formulae 7-10. The list is for illustrativepurposes only and should not be construed to be limiting in any way. Anumber of final components may be formed by permuting all possiblecombinations of the constituent moieties with each other. Whenhydrocarbyl radicals including alkyl, alkenyl, alkynyl, cycloalkyl,cycloalkenyl, cycloalkynyl and aromatic radicals are disclosed in thisapplication the term includes all isomers. For example, butyl includesn-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl;pentyl includes n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1-ethylpropyl, neopentyl, cyclopentyl and methylcyclobutyl; butenylincludes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl. This includes when a radical is bonded to anothergroup, for example, propylcyclopentadienyl includen-propylcyclopentadienyl, isopropylcyclopentadienyl andcyclopropylcyclopentadienyl. In general, the ligands or groupsillustrated in Table A include all isomeric forms. For example,dimethylcyclopentadienyl includes 1,2-dimethylcyclopentadienyl and1,3-dimethylcyclopentadienyl; methylindenyl includes 1-methylindenyl,2-methylindenyl, 3-methylindenyl, 4-methylindenyl, 5-methylindenyl,6-methylindenyl and 7-methylindenyl; methylethylphenyl includesortho-methylethylphenyl, meta-methylethylphenyl andpara-methylethylphenyl. Examples of specific invention catalystprecursors take the following formula where some components are listedin Table A. To illustrate members of the transition metal component,select any combination of the species listed in Tables A. Fornomenclature purposes, for the bridging group, A′, the words “silyl” and“silylene” are used interchangeably, and represent a diradical species.For the bridging group A′, “ethylene” refers to a 1,2-ethylene linkageand is distinguished from ethene-1,1-diyl. Thus, for the bridging groupA′, “ethylene” and “1,2-ethylene” are used interchangeably. Forcompounds processing a bridging group, A′, the bridge position on thecyclopentadienyl-type ring is always considered the 1-position. Thus,for example, the use of “1-fluorenyl” is interchangeable with the use of“fluorenyl”

[0265] Illustrative compounds of the formula 8 type are:bis(cyclopentadienyl)hafnium dimethyl,ethylenebis(tetrahydroindenyl)zirconium dihidryde,bis(pentamethyl)zirconium diethyl,dimethylsilyl(1-fluorenyl)(cyclopentadienyl)titanium dichloride and thelike. Illustrative compounds of the formula 9 type are:bis(cyclopentadienyl)(1,3-butadiene)zirconium,bis(cyclopentadienyl)(2,3-dimethyl-1,3-butadiene)zirconium,bis(pentamethylcyclopentadienyl)(benzene)zirconium,bis(pentamethylcyclopentadienyl)titanium ethylene and the like.Illustrative compounds of the formula 10 type are:dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)zirconiumdichloride, ethylene(methylcyclopentadienyl)(phenylamido)titaniumdimethyl, methylphenylsilyl(indenyl)(phenyphosphido)hafnium dihydrideand (pentamethylcyclopentadienyl)(di-t-butylamido)hafnium dimethoxide.

[0266] The conditions under which complexes containing neutral Lewisbase ligands such as ether or those which form dimeric compounds isdetermined by the steric bulk of the ligands about the metal center. Forexample, the t-butyl group in Me₂Si(Me₄C₅)(N-t-Bu)ZrCl₂ has greatersteric requirements that the phenyl in Me₂Si(Me₄C₅)(NPh)ZrCl₂.Et₂Othereby not permitting ether coordination in the former compound in itssolid state. Similarly, due to the decreased steric bulk of thetrimethylsilylcyclopentadienyl group in [Me₂Si(Me₃SiC₅H₃)(N-t-Bu)ZrCl₂]₂versus that of the tetramethylcyclopentadienyl group inMe₂Si(Me₄C₅)(N-t-Bu)ZrCl₂, the former compound is dimeric and the latteris not. TABLE A A′ Dimethylsilylene Diethylsilylene DipropylsilyleneDibutylsilylene Dipentylsilylene Dihexylsilylene DiheptylsilyleneDioctylsilylene Dinonylsilylene Didecylsilylene DiundecylsilyleneDidodecylsilylene Ditridecylsilylene DitetradecylsilyleneDipentadecylsilylene Dihexadecylsilylene DiheptadecylsilyleneDioctadecylsilylene Dinonadecylsilylene DieicosylsilyleneDiheneicosylsilylene Didocosylsilylene DitricosylsilyleneDitetracosylsilylene Dipentacosylsilylene DihexacosylsilyleneDiheptacosylsilylene Dioctacosylsilylene DinonacosylsilyleneDitriacontylsilylene Dicyclohexylsilylene DicyclopentylsilyleneDicycloheptylsilylene Dicyclooctylsilylene DicyclodecylsilyleneDicyclododecylsilylene Dinapthylsilylene DiphenylsilyleneDitolylsilylene Dibenzylsilylene Diphenethylsilylenedi(butylphenethyl)silylene Methylethylsilylene MethylpropylsilyleneMethylbutylsilylene Methylhexylsilylene MethylphenylsilyleneEthylphenylsilylene Ethylpropylsilylene EthylbutylsilylenePropylphenylsilylene Dimethylgermylene DiethylgermyleneDiphenylgermylene Methylphenylgermylene CyclotetramethylenesilyleneCyclopentamethylenesilylene CyclotrimethylenesilyleneCyclohexylazanediyl Butylazanediyl Methylazanediyl PhenylazanediylPerfluorophenylazanediyl Methylphosphanediyl EthylphosphanediylPropylphosphanediyl Butylphosphanediyl CyclohexylphosphanediylPhenylphosphanediyl Methylboranediyl Phenylboranediyl MethyleneDimethylmethylene Diethylmethylene Dibutylmethylene DipropylmethyleneDiphenylmethylene Ditolylmethylene di(butylphenyl)methylenedi(trimethylsilylphenyl)methylene di(triethylsilylphenyl)methyleneDibenzylmethylene CyclotetramethylenemethyleneCyclopentamethylenemethylene Ethylene Methylethylene DimethylethyleneTrimethylethylene Tetramethylethylene Cyclopentylene CyclohexyleneCycloheptylene Cyclooctylene Propanediyl MethylpropanediylDimethylpropanediyl Trimethylpropanediyl TetramethylpropanediylPentamethylpropanediyl Hexamethylpropanediyl TetramethyldisiloxyleneVinylene ethene-1,1-diyl Divinylsilylene DipropenylsilyleneDibutenylsilylene Methylvinylsilylene MethylpropenylsilyleneMethylbutenylsilylene Dimethylsilylmethylene DiphenylsilylmethyleneDimethylsilylethylene Diphenylsilylethylene DimethylsilylpropyleneDiphenylsilylpropylene Dimethylstannylene Diphenylstannylene Cp, Cp*,CpR or (C₅H_(5-y-x)S″_(x)) cyclopentadienyl methylcyclopentadienyldimethylcyclopentadienyl trimethylcyclopentadienyltetramethylcyclopentadienyl pentamethylcyclopentadienyl (no A′)ethylcyclopentadienyl diethylcyclopentadienyl propylcyclopentadienyldipropylcyclopentadienyl butylcyclopentadienyl dibutylcyclopentadienylpentylcyclopentadienyl dipentylcyclopentadienyl hexylcyclopentadienyldihexylcyclopentadienyl heptylcyclopentadienyl diheptylcyclopentadienyloctylcyclopentadienyl dioctylcyclopentadienyl nonylcyclopentadienyldinonylcyclopentadienyl decylcyclopentadienyl didecylcyclopentadienylundecylcyclopentadienyl dodecylcyclopentadienyl tridecylcyclopentadienyltetradecylcyclopentadienyl pentadecylcyclopentadienyl (no A′)hexadecylcyclopentadienyl heptadecylcyclopentadienyloctadecylcyclopentadienyl nonadecylcyclopentadienyleicosylcyclopentadienyl heneicosylcyclopentadienyldocosylcyclopentadienyl tricosylcyclopentadienyltetracosylcyclopentadienyl pentacosylcyclopentadienylhexacosylcyclopentadienyl heptacosylcyclopentadienyloctacosylcyclopentadienyl nonacosylcyclopentadienyltriacontylcyclopentadienyl cyclohexylcyclopentadienylphenylcyclopentadienyl diphenylcyclopentadienyltriphenylcyclopentadienyl tetraphenylcyclopentadienylpentaphenylcyclopentadienyl tolylcyclopentadineyl benzylcyclopentadienylphenethylcyclopentadienyl cyclohexylmethylcyclopentadienylnapthylcyclopentadienyl methylphenylcyclopentadienylmethyltolylcyclopentadienyl methylethylcyclopentadienylmethylpropylcyclopentadienyl methylbutylcyclopentadienylmethylpentylcyclopentadienyl methylhexylcyclopentadienylmethylheptylcyclpentadienyl methyloctylcyclopentadienylmethylnonylcyclopentadienyl methyldecylcyclopentadienylvinylcyclopentadienyl propenylcyclopentadienyl butenylcyclopentadienylindenyl methylindenyl dimethylindenyl trimethylindenylmethylpropylindenyl dimethylpropylindenyl methyldipropylindenylmethylethylindenyl methylbutylindenyl ethylindenyl propylindenylbutylindenyl pentylindenyl hexylindenyl heptylindenyl octylindenylnonylindenyl decylindenyl phenylindenyl (fluorophenyl)indenyl(methylphenyl)indenyl biphenylindenyl(bis(trifluoromethyl)phenyl)indenyl napthylindenyl phenanthrylindenylbenzylindenyl benzindenyl cyclohexylindenyl methylphenylindenylethylphenylindenyl propylphenylindenyl methylnapthylindenylethylnapthylindenyl propylnapthylindenyl (methylphenyl)indenyl(dimethylphenyl)indenyl (ethylphenyl)indenyl (diethylphenyl)indenyl(propylphenyl)indenyl (dipropylphenyl)indenyl methyltetrahydroindenyldimethyltetrahydroindenyl dimethyldihydroindenyl dimethyltrihydroindenylmethylphenyltetrahydroindenyl methylphenyldihydroindenylmethylphenyltrihydroindenyl ethyltetrahydroindenylpropyltetrahydroindenyl butyltetrahydroindenyl PhenyltetrahydroindenylFluorenyl Methylfluorenyl Dimethylfluorenyl TrimethylfluorenylEthylfluorenyl Propylfluorenyl Butylfluorenyl DibutylfluorenylPentylfluorenyl Hexylfluorenyl Heptylfluorenyl OctylfluorenylNonylfluorenyl Decylfluorenyl Phenylfluorenyl NapthylfluorenylBenzylfluorenyl Methylphenylfluorenyl EthylphenylfluorenylPropylphenylfluorenyl Methylnapthylfluorenyl EthylnapthylfluorenylPropylnapthylfluorenyl Octahydrofluorenyl tetrahydrofluorenyloctamethyloctahydrodibenzo[b,h]fluorenylTetramethyltetrahydrobenzo[b]fluorenyl DiphenylmethylcyclopentadienylTrimethylsilylcyclopentadienyl TriethylsilylcyclopentadienylTrimethylgermylcyclopentadienyl TrimethylstannylcyclopentadienylTriethylplumbylcyclopentadienyl TrifluromethylcyclopentadienylN,N-dimethylamidocyclopentadienyl P,P-dimethylphosphidocyclopentadienylN,N-diethylamidocyclopentadienyl MethoxycyclopentadienylEthoxycyclopentadienyl trimethylsiloxycyclopentadienyl (N,N-Methyoxyindenyl Dimethyoxyindenyl N,N-dimethylaminoindenylTrimethylsiloxyindenyl Butyldimethylsiloxyindenylbis(N,N-dimethylamino)indenyl di(trimethylsiloxy)indenyldi(butyldimethylsiloxy)indenyl Methoxyfluorenyl DimethoxyfluorenylN,N-dimethylaminofluorenyl TrimethylsiloxyfluorenylButyldimethylsiloxyfluorenyl Dimethoxyfluorenylbis(N,N-dimethylamino)fluorenyl di(trimethylsiloxy)fluorenyldi(butyldimethylsiloxy)fluorenyl (JS′_(z-1-y)) (y = 1) MethylamidoEthylamido Propylamido Butylamido Pentylamido Hexylamido HeptylamidoOctylamido Nonylamido Decylamido Eicosylamido HeneicosylamidoDocosylamido Tricosylamido Tetracosylamido PentacosylamidoHexacosylamido Heptacosylamido Octacosylamido NonacosylamidoTriacontylamido Phenylamido Tolylamido Phenethylamido BenzylamidoCyclobutylamido Cyclopentylamido Cyclohexylamido CycloheptylamidoCyclooctylamido Cyclononylamido Cyclodecylamido CyclododecylamidoAdamantylamido Norbornylamido Perfluorophenylamido FluorophenylamidoDifluorophenylamido Oxo Sulfido (JS′_(z-1-y)) (y = 0) Methoxide EthoxidePhenoxide Dimethylphenoxide Dipropylphenoxide Methylthio EthylthioPhenylthio Dimethylphenylthio Dipropylphenylthio X₁ or X₂ ChlorideBromide Iodide Fluoride Hydride Methyl Ethyl Propyl Butyl Pentyl HexylHeptyl Octyl Nonyl Decyl Undecyl Dodecyl Tridecyl Tetradecyl PentadecylHexadecyl Heptadecyl Octadecyl Nonadecyl Eicosyl Heneicosyl DocosylTricosyl Tetracosyl Pentacosyl Hexacosyl Heptacosyl Octacosyl NonacosylTriacontyl Phenyl Benzyl Phenethyl Tolyl Methoxy Ethoxy Propoxy ButoxyDimethylamido Diethylamido Methylethylamido Phenoxy Benzoxy Allyl X₁ andX₂ together methylidene Ethylidene Propylidene TetramethylenePentamethylene Hexamethylene Ethylenedihydroxy Butadiene MethylbutadieneDimethylbutadiene Pentadiene Methylpentadiene DimethylpentadieneHexadiene Methylhexadiene Dimethylhexadiene M titanium zirconium hafniumL or L′ (optional) ethylene propylene butene hexene styrene hexadienebutadiene dimethylbutadiene pentadiene methylhexadiene dimethylhexadieneacetylene methylacetylene ethylacetylene benzyne cyclopentenecyclohexene L′ (optional) diethylether dimethylether trimethylaminetriphenylamine triethylamine tricyclohexylphosp triphenylphosphinetrimethylphosphin tetrahydrofuran furan thiophene dimethylsulfidediphenylsulfide

[0267] Additional preferred catalysts include those described in WO01/48034, which is incorporated herein by reference. Particularlypreferred catalyst compounds include those disclosed at page 9, line 38to page 25, line 42, page 28, lines 5 to 17, and page 30, line 37 topage 35, line 28.

[0268] Activators and Activation Methods for Catalyst Compounds

[0269] The polymerization pre-catalyst compounds, described above, aretypically activated in various ways to yield compounds having a vacantcoordination site that will coordinate, insert, and polymerizeolefin(s). For the purposes of this patent specification and appendedclaims, the terms “cocatalyst” and “activator” are used hereininterchangeably and are defined to be any compound which can activateany one of the catalyst compounds described above by converting theneutral catalyst compound to a catalytically active catalyst compoundcation. Non-limiting activators, for example, include alumoxanes,aluminum alkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract one reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

[0270] Aluminoxane and Aluminum Alkyl Activators

[0271] In one embodiment, alumoxane activators are utilized as anactivator in the catalyst composition useful in the invention.Alumoxanes are generally oligomeric compounds containing —Al(R¹)—O—sub-units, where R¹ is an alkyl group. Examples of alumoxanes includemethylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxaneand isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes aresuitable as catalyst activators, particularly when the abstractableligand is a halide, alkoxide or amide. Mixtures of different alumoxanesand modified alumoxanes may also be used.

[0272] The activator compounds comprising Lewis-acid activators and inparticular alumoxanes are represented by the following general formulae:

(R³—Al—O)_(p)  (11)

R⁴(R⁵—Al—O)_(p)-AlR⁶ ₂  (12)

(M′)^(m+)Q′_(m)  (13)

[0273] An alumoxane is generally a mixture of both the linear and cycliccompounds. In the general alumoxane formula, R³, R⁴, R⁵ and R⁶ are,independently a C₁-C₃₀ alkyl radical, for example, methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and “p” is aninteger from 1 to about 50. Most preferably, R³, R⁴, R⁵ and R⁶ are eachmethyl and “p” is a least 4. When an alkyl aluminum halide or alkoxideis employed in the preparation of the alumoxane, one or more R³⁻⁶ groupsmay be halide or alkoxide. M′ is a metal or metalloid, and Q′ is apartially or fully fluorinated hydrocarbyl.

[0274] It is recognized that alumoxane is not a discrete material. Atypical alumoxane will contain free trisubstituted or trialkyl aluminum,bound trisubstituted or trialkyl aluminum, and alumoxane molecules ofvarying degree of oligomerization. Those methylalumoxanes most preferredcontain lower levels of trimethylaluminum. Lower levels oftrimethylaluminum can be achieved by reaction of the trimethylaluminumwith a Lewis base or by vacuum distillation of the trimethylaluminum orby any other means known in the art. It is also recognized that afterreaction with the transition metal compound, some alumoxane moleculesare in the anionic form as represented by the anion in equations 4-6,thus for our purposes are considered “non-coordinating” anions.

[0275] For further descriptions, see U.S. Pat. Nos. 4,665,208,4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081,5,157,137, 5,103,031 and EP 0 561 476 A1, EP 0 279 586 B1, EP0 516 476A, EP 0 594 218 A1 and WO 94/10180.

[0276] When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst precursor (per metal catalytic site). Theminimum activator-to-catalyst-precursor is a 1:1 molar ratio.

[0277] Alumoxanes may be produced by the hydrolysis of the respectivetrialkylaluminum compound. MMAO may be produced by the hydrolysis oftrimethylaluminum and a higher trialkylaluminum such astriisobutylaluminum. MMAO's are generally more soluble in aliphaticsolvents and more stable during storage. There are a variety of methodsfor preparing alumoxane and modified alumoxanes, non-limiting examplesof which are described in U.S. Pat. Nos. 4,665,208, 4,952,540,5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463,4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137,5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451,5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and Europeanpublications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0586 665, and PCT publications WO 94/10180 and WO 99/15534, all of whichare herein fully incorporated by reference. It may be preferable to usea visually clear methylalumoxane. A cloudy or gelled alumoxane can befiltered to produce a clear solution or clear alumoxane can be decantedfrom the cloudy solution. Another alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from AkzoChemicals, Inc. under the trade name Modified Methylalumoxane type 3A,covered under patent number U.S. Pat. No. 5,041,584).

[0278] Aluminum alkyl or organoaluminum compounds which may be utilizedas activators (or scavengers) include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

[0279] Ionizing Activators

[0280] It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammoniumtetrakis (pentafluorophenyl)boron, a trisperfluorophenyl boron metalloidprecursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

[0281] Examples of neutral stoichiometric activators includetri-substituted boron, tellurium, aluminum, gallium and indium ormixtures thereof. The three substituent groups are each independentlyselected from alkyls, alkenyls, halogen, substituted alkyls, aryls,arylhalides, alkoxy and halides. Preferably, the three groups areindependently selected from halogen, mono or multicyclic (includinghalosubstituted) aryls, alkyls, and alkenyl compounds and mixturesthereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkylgroups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbonatoms and aryl groups having 3 to 20 carbon atoms (including substitutedaryls). More preferably, the three groups are alkyls having 1 to 4carbon groups, phenyl, napthyl or mixtures thereof. Even morepreferably, the three groups are halogenated, preferably fluorinated,aryl groups. Most preferably, the neutral stoichiometric activator istrisperfluorophenyl boron or trisperfluoronapthyl boron.

[0282] Ionic stoichiometric activator compounds may contain an activeproton, or some other cation associated with, but not coordinated to, oronly loosely coordinated to, the remaining ion of the ionizing compound.Such compounds and the like are described in European publicationsEP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401,5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

[0283] Ionic catalysts can be preparedly reacting a transition metalcompound with some neutral Lewis acids, such as B(C₆F₆)₃, which uponreaction with the hydrolyzable ligand (X) of the transition metalcompound forms an anion, such as ([B(C₆F₅)₃(X)]⁻), which stabilizes thecationic transition metal species generated by the reaction. Thecatalysts can be, and preferably are, prepared with activator componentswhich are ionic compounds or compositions. However preparation ofactivators utilizing neutral compounds is also contemplated by thisinvention.

[0284] Compounds useful as an activator component in the preparation ofthe ionic catalyst systems used in the process of this inventioncomprise a cation, which is preferably a Bronsted acid capable ofdonating a proton, and a compatible non-coordinating anion which anionis relatively large (bulky), capable of stabilizing the active catalystspecies (the Group 4 cation) which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, nitrites and the like. Two classesof compatible non-coordinating anions have been disclosed in EPA 277,003and EPA 277,004 published 1988: 1) anionic coordination complexescomprising a plurality of lipophilic radicals covalently coordinated toand shielding a central charge-bearing metal or metalloid core, and 2)anions comprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

[0285] In a preferred embodiment, the stoichiometric activators includea cation and an anion component, and may be represented by the followingformula:

(L-H)_(d) ⁺(A^(d−))  (14)

[0286] wherein L is an neutral Lewis base;

[0287] H is hydrogen;

[0288] (L-H)⁺ is a Bronsted acid

[0289] A^(d−) is a non-coordinating anion having the charge d−

[0290] d is an integer from 1 to 3.

[0291] The cation component, (L-H)d+may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thebulky ligand metallocene containing transition metal catalyst precursor,resulting in a cationic transition metal species.

[0292] The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capableof donating a proton to the transition metal catalytic precursorresulting in a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof. The activating cation (L-H)_(d) ⁺ may also be a moietysuch as silver, tropylium, carbeniums, ferroceniums and mixtures,preferably carboniums and ferroceniums. Most preferably (L-H)_(d) ⁺ istriphenyl carbonium.

[0293] The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

[0294] Illustrative, but not limiting examples of boron compounds whichmay be used as an activating cocatalyst in the preparation of theimproved catalysts of this invention are tri-substituted ammonium saltssuch as: trimethylammonium tetraphenylborate, triethylammoniumtetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronapthyl)borate, triethylammoniumtetrakis(perfluoronapthyl)borate, tripropylammoniumtetrakis(perfluoronapthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronapthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronapthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronapthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronapthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronapthyl)borate,tropillium tetrakis(perfluoronapthyl)borate, triphenylcarbeniumtetrakis(perfluoronapthyl)borate, triphenylphosphoniumtetrakis(perfluoronapthyl)borate, triethylsilyliumtetrakis(perfluoronapthyl)borate,benzene(diazonium)tetrakis(perfluoronapthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, anddialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and additional tri-substitutedphosphonium salts such as tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

[0295] Most preferably, the ionic stoichiometric activator (L-H)_(d) ⁺(A^(d−)) is N,N-dimethylanilinium tetra(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronapthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronapthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

[0296] In one embodiment, an activation method using ionizing ioniccompounds not containing an active proton but capable of producing abulky ligand metallocene catalyst cation and their non-coordinatinganion are also contemplated, and are described in EP-A-0 426 637, EP-A-0573 403 and U.S. Pat. No. 5,387,568, which are all herein incorporatedby reference.

[0297] The term “non-coordinating anion” (NCA) means an anion whicheither does not coordinate to said cation or which is only weaklycoordinated to said cation thereby remaining sufficiently labile to bedisplaced by a neutral Lewis base. “Compatible” non-coordinating anionsare those which are not degraded to neutrality when the initially formedcomplex decomposes. Further, the anion will not transfer an anionicsubstituent or fragment to the cation so as to cause it to form aneutral four coordinate metallocene compound and a neutral by-productfrom the anion. Non-coordinating anions useful in accordance with thisinvention are those that are compatible, stabilize the metallocenecation in the sense of balancing its ionic charge at +1, yet retainsufficient lability to permit displacement by an ethylenically oracetylenically unsaturated monomer during polymerization. These types ofcocatalysts sometimes use tri-isobutyl aluminum or tri-octyl aluminum asa scavenger.

[0298] Invention process also can employ cocatalyst compounds oractivator compounds that are initially neutral Lewis acids but form acationic metal complex and a noncoordinating anion, or a zwitterioniccomplex upon reaction with the invention compounds. For example,tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbylor hydride ligand to yield an invention cationic metal complex andstabilizing noncoordinating anion, see EP-A-0 427 697 and EP-A-0 520 732for illustrations of analogous Group-4 metallocene compounds. Also, seethe methods and compounds of EP-A-0 495 375. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

[0299] When the cations of noncoordinating anion precursors are Bronstedacids such as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation. For example, tris(perfluorophenyl) boron can beused with methylalumoxane.

[0300] Conventional-Type Cocatalysts (Activators)

[0301] Typically, conventional transition metal catalyst compoundsexcluding some conventional-type chromium catalyst compounds areactivated with one or more of the conventional cocatalysts which may berepresented by the formula:

M³M⁴ _(v)X² _(c)R² _(b−c)  (15)

[0302] wherein M³ is a metal from Group 1 to 3 and 12 to 13 of thePeriodic Table of Elements; M⁴ is a metal of Group 1 of the PeriodicTable of Elements; v is a number from 0 to 1; each X² is any halogen; cis a number from 0 to 3; each R² is a monovalent hydrocarbon radical orhydrogen; b is a number from 1 to 4; and wherein b minus c is atleast 1. Other conventional-type organometallic cocatalyst compounds forthe above conventional-type transition metal catalysts have the formulaM³R² _(k), where M³ is a Group IA, IIA, IIB or IIIA metal, such aslithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, andgallium; k equals 1, 2 or 3 depending upon the valency of M³ whichvalency in turn normally depends upon the particular Group to which M³belongs; and each R² may be any monovalent hydrocarbon radical.

[0303] Non-limiting examples of conventional-type organometalliccocatalyst compounds useful with the conventional-type catalystcompounds described above include methyllithium, butyllithium,dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium,diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminumalkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum,and tri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude mono-organohalides and hydrides of Group 2 metals, and mono- ordi-organohalides and hydrides of Group 3 and 13 metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide,di-isobutylaluminum hydride, methylcadmium hydride, diethylboronhydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesiumhydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminumhydride and bromocadmium hydride. Conventional-type organometalliccocatalyst compounds are known to those in the art and a more completediscussion of these compounds may be found in U.S. Pat. Nos. 3,221,002and 5,093,415, which are herein fully incorporated by reference.

[0304] Additional Activators

[0305] Other activators include those described in PCT publication WO98/07515 such as tris(2,2′, 2″-nonafluorobiphenyl)fluoroaluminate, whichpublication is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference.

[0306] Other suitable activators are disclosed in WO 98/09996,incorporated herein by reference, which describes activating bulkyligand metallocene catalyst compounds with perchlorates, periodates andiodates including their hydrates. WO 98/30602 and WO 98/30603,incorporated by reference, describe the use of lithium(2,2′-bisphenyl-ditrimethylsilicate)·4THF as an activator for a bulkyligand metallocene catalyst compound. WO 99/18135, incorporated hereinby reference, describes the use of organo-boron-aluminum activators.EP-B 1-0 781 299 describes using a silylium salt in combination with anon-coordinating compatible anion. Also, methods of activation such asusing radiation (see EP-B 1-0 615 981 herein incorporated by reference),electro-chemical oxidation, and the like are also contemplated asactivating methods for the purposes of rendering the neutral bulkyligand metallocene catalyst compound or precursor to a bulky ligandmetallocene cation capable of polymerizing olefins. Other activators ormethods for activating a bulky ligand metallocene catalyst compound aredescribed in for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and5,869,723 and WO 98/32775, WO 99/42467(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are herein incorporated by reference.

[0307] Another suitable ion forming, activating cocatalyst comprises asalt of a cationic oxidizing agent and a noncoordinating, compatibleanion represented by the formula:

(OX^(e+))_(d)(A^(d−))_(e)  (16)

[0308] wherein OX^(e+) is a cationic oxidizing agent having a charge ofe+; e is an integer from 1 to 3; and A⁻, and d are as previouslydefined. Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

[0309] It is within the scope of this invention that catalyst compoundscan be combined one or more activators or activation methods describedabove. For example, a combination of activators have been described inU.S. Pat. Nos. 5,153,157 and 5,453,410, European publication EP-B1 0 573120, and PCT publications WO 94/07928 and WO 95/14044. These documentsall discuss the use of an alumoxane and an ionizing activator with abulky ligand metallocene catalyst compound.

[0310] The Choice of Transition Metal Catalyst Components

[0311] The catalyst system of this invention comprises two or moretransition metal compounds as described above. At least one of thecompounds must be capable of producing a crystalline poly-alpha-olefin,preferably isotactic polypropylene or syndiotactic polypropylene, havinga crystallinity of 40% or more. The other compound must be capable ofproducing an amorphous poly-alpha-olefin, preferably atacticpolypropylene, having a crystallinity of 20% or less.

[0312] The choice of transition metal component for the crystallinepolymer fraction is a subset of the transition metal component ofequations 8-9. This preferred component is illustrated in equation 17:

[0313] wherein A′, M, X₁ and X₂ are as previously defined. SubstituentsS″_(v) are independently defined as S″ in equations 8-9 where thesubscript “v” denotes the carbon atom on the Cp-ring to which thesubstituent is bonded.

[0314] Preferably metallocene precursors for producing poly-alpha-olefins having enhanced isotactic character are those of Equation17 where S″_(v) are independently chosen such that the metalloceneframework 1) has no plane of symmetry containing the metal center, and2) has a C₂-axis of symmetry through the metal center. Such complexes,such as rac-Me₂Si(indenyl)₂ZrMe₂ and rac-Me₂Si(indenyl)₂HfMe₂ are wellknown in the art and generally produce isotactic polymers with higherdegrees of stereoregularity than the less symmetric chiral systems.Likewise another preferred class of transition metal compounds that canproduce isotactic polymers useful in this invention are thosemonocyclopentadienyl catalysts disclosed in U.S. Pat. No. 5,026,798,which is incorporated by reference herein.

[0315] Preferred chiral racemic metallocene compounds which, accordingto the present invention, provide catalyst systems which are specific tothe production of isotactic poly- alpha-olefins include the racemicversions of:

[0316] dimethylsilylbis(indenyl)zirconium dichloride,dimethylsilylbis(indenyl) zirconium dimethyl,diphenylsilylbis(indenyl)zirconium dichloride,

[0317] diphenylsilylbis(indenyl)zirconium dimethyl,methylphenylsilylbis(indenyl) zirconium dichloride,

[0318] methylphenylsilylbis(indenyl)zirconium dimethyl,ethylenebis(indenyl) zirconium dichloride, ethylenebis(indenyl)zirconiumdimethyl,

[0319] methylenebis(indenyl)zirconium dichloride,methylenebis(indenyl)zirconium dimethyl,dimethylsilylbis(indenyl)hafnium dichloride, dimethylsilylbis(indenyl)

[0320] hafnium dimethyl, diphenylsilylbis(indenyl)hafnium dichloride,diphenylsilylbis(indenyl)hafnium dimethyl, methylphenylsilylbis(indenyl)

[0321] hafnium dichloride, methylphenylsilylbis(indenyl)hafniumdimethyl,

[0322] ethylenebis(indenyl)hafnium dichloride,ethylenebis(indenyl)hafnium dimethyl,

[0323] methylenebis(indenyl)hafnium dichloride,methylenebis(indenyl)hafnium dimethyl,dimethylsilylbis(tetrahydroindenyl)zirconium dichloride,

[0324] dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[0325] diphenylsilylbis(tetrahydroindenyl)zirconium dichloride,

[0326] diphenylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[0327] methylphenylsilylbis(tetrahydroindenyl)zirconium dichloride,

[0328] methylphenylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[0329] ethylenebis(tetrahydroindenyl)zirconium dichloride,

[0330] ethylenebis(tetrahydroindenyl)zirconium dimethyl,

[0331] methylenebis(tetrahydroindenyl)zirconium dichloride,

[0332] methylenebis(tetrahydroindenyl)zirconium dimethyl,

[0333] dimethylsilylbis(tetrahydroindenyl)hafnium dichloride,

[0334] dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[0335] diphenylsilylbis(tetrahydroindenyl)hafnium dichloride,

[0336] diphenylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[0337] methylphenylsilylbis(tetrahydroindenyl)hafnium dichloride,

[0338] methylphenylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[0339] ethylenebis(tetrahydroindenyl)hafnium dichloride,ethylenebis(tetrahydroindenyl)

[0340] hafnium dimethyl, methylenebis(tetrahydroindenyl)hafniumdichloride,

[0341] methylenebis(tetrahydroindenyl)hafnium dimethyl,dimethylsilylbis(2-methylindenyl)zirconium dichloride,dimethylsilylbis(2-methylindenyl) zirconium dimethyl,diphenylsilylbis(2-methylindenyl)zirconium dichloride,

[0342] diphenylsilylbis(2-methylindenyl)zirconium dimethyl,methylphenylsilylbis(2-methylindenyl)zirconium dichloride,methylphenylsilylbis(2-methylindenyl) zirconium dimethyl,ethylenebis(2-methylindenyl)zirconium dichloride,

[0343] ethylenebis(2-methylindenyl)zirconium dimethyl,methylenebis(2-methylindenyl) zirconium dichloride,methylenebis(2-methylindenyl)zirconium dimethyl,

[0344] dimethylsilylbis(2-methylindenyl)hafnium dichloride,dimethylsilylbis(2-methylindenyl)hafnium dimethyl,diphenylsilylbis(2-methylindenyl)hafnium dichloride,diphenylsilylbis(2-methylindenyl)hafnium dimethyl,

[0345] methylphenylsilylbis(2-methylindenyl)hafnium dichloride,

[0346] methylphenylsilylbis(2-methylindenyl)hafnium dimethyl,ethylenebis(2-methylindenyl)hafnium dichloride,ethylenebis(2-methylindenyl)hafnium dimethyl,methylenebis(2-methylindenyl)hafnium dichloride,methylenebis(2-methylindenyl)hafnium dimethyl,rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride,diphenylsilylbis(2-methyl-4-phenylindenyl) zirconium dimethyl,diphenylsilylbis(2-methyl-4-phenylindenyl)zirconium

[0347] dichloride, diphenylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

[0348] methylphenylsilylbis(2-methyl-4-phenylindenyl)zirconiumdichloride,

[0349] methylphenylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,

[0350] ethylenebis(2-methyl-4-phenylindenyl)zirconium dichloride,ethylenebis(2-methyl-4-phenylindenyl)zirconium dimethyl,methylenebis(2-methyl-4-phenylindenyl)zirconium dichloride,methylenebis(2-methyl-4-phenylindenyl) zirconium dimethyl,dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride,dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dimethyl,

[0351] diphenylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride,

[0352] diphenylsilylbis(2-methyl-4-phenylindenyl)hafnium dimethyl,

[0353] methylphenylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride,

[0354] methylphenylsilylbis(2-methyl-4-phenylindenyl)hafnium dimethyl,

[0355] ethylenebis(2-methyl-4-phenylindenyl)hafnium dichloride,ethylenebis(2-methyl-4-phenylindenyl)hafnium dimethyl,methylenebis(2-methyl-4-phenylindenyl) hafnium dichloride,methylenebis(2-methyl-4-phenylindenyl)hafnium dimethyl,

[0356] dimethylsilylbis(4,7-dimethylindenyl)zirconium dichloride,dimethylsilylbis(4,7-dimethylindenyl)zirconium dimethyl,diphenylsilylbis(4,7-dimethylindenyl) zirconium dichloride,diphenylsilylbis(4,7-dimethylindenyl)zirconium dimethyl,

[0357] methylphenylsilylbis(4,7-dimethylindenyl)zirconium dichloride,

[0358] methylphenylsilylbis(4,7-dimethylindenyl)zirconium dimethyl,ethylenebis(4,7-dimethylindenyl)zirconium dichloride,ethylenebis(4,7-dimethylindenyl) zirconium dimethyl,methylenebis(4,7-dimethylindenyl)zirconium dichloride,

[0359] methylenebis(4,7-dimethylindenyl)zirconium dimethyl,dimethylsilylbis(4,7-dimethylindenyl)hafnium dichloride,dimethylsilylbis(4,7-dimethylindenyl) hafnium dimethyl,diphenylsilylbis(4,7-dimethylindenyl)hafnium dichloride,

[0360] diphenylsilylbis(4,7-dimethylindenyl)hafnium dimethyl,

[0361] methylphenylsilylbis(4,7-dimethylindenyl)hafnium dichloride,

[0362] methylphenylsilylbis(4,7-dimethylindenyl)hafnium dimethyl,ethylenebis(4,7-dimethylindenyl)hafnium dichloride,ethylenebis(4,7-dimethylindenyl)hafnium dimethyl,methylenebis(4,7-dimethylindenyl)hafnium dichloride,

[0363] methylenebis(4,7-dimethylindenyl)hafnium dimethyl,dimethylsilylbis(2-methyl-4-napthylindenyl)zirconium dichloride,dimethylsilylbis(2-methyl-4-napthylindenyl)zirconium dimethyl,diphenylsilylbis(2-methyl-4-napthylindenyl) zirconium dichloride,diphenylsilylbis(2-methyl-4-napthylindenyl)zirconium dimethyl,methylphenylsilylbis(2-methyl-4-napthylindenyl)zirconium dichloride,

[0364] methylphenylsilylbis(2-methyl-4-napthylindenyl)zirconiumdimethyl,

[0365] ethylenebis(2-methyl-4-napthylindenyl)zirconium dichloride,ethylenebis(2-methyl-4-napthylindenyl)zirconium dimethyl,methylenebis(2-methyl-4-napthylindenyl)zirconium dichloride,methylenebis(2-methyl-4-napthylindenyl) zirconium dimethyl,dimethylsilylbis(2-methyl-4-napthylindenyl)hafnium dichloride,dimethylsilylbis(2-methyl-4-napthylindenyl)hafnium dimethyl,

[0366] diphenylsilylbis(2-methyl-4-napthylindenyl)hafnium dichloride,

[0367] diphenylsilylbis(2-methyl-4-napthylindenyl)hafnium dimethyl,

[0368] methylphenylsilylbis(2-methyl-4-napthylindenyl)hafniumdichloride,

[0369] methylphenylsilylbis(2-methyl-4-napthylindenyl)hafnium dimethyl,

[0370] ethylenebis(2-methyl-4-napthylindenyl)hafnium dichloride,ethylenebis(2-methyl-4-napthylindenyl)hafnium dimethyl,methylenebis(2-methyl-4-napthylindenyl)hafnium dichloride,methylenebis(2-methyl-4-napthylindenyl) hafnium dimethyl,dimethylsilylbis(2,3-dimethylcyclopentadienyl)zirconium dichloride,dimethylsilylbis(2,3-dimethylcyclopentadienyl)zirconium dimethyl,

[0371] diphenylsilylbis(2,3-dimethylcyclopentadienyl)zirconiumdichloride,

[0372] diphenylsilylbis(2,3-dimethylcyclopentadienyl)zirconium dimethyl,

[0373] methylphenylsilylbis(2,3-dimethylcyclopentadienyl)zirconiumdichloride,

[0374] methylphenylsilylbis(2,3-dimethylcyclopentadienyl)zirconiumdimethyl,

[0375] ethylenebis(2,3-dimethylcyclopentadienyl)zirconium dichloride,ethylenebis(2,3-dimethylcyclopentadienyl)zirconium dimethyl,methylenebis(2,3-dimethylcyclopentadienyl)zirconium dichloride,methylenebis(2,3-dimethylcyclopentadienyl)zirconium dimethyl,dimethylsilylbis(2,3-dimethylcyclopentadienyl)hafnium dichloride,dimethylsilylbis(2,3 dimethylcyclopentadienyl)hafnium dimethyl,diphenylsilylbis(2,3-dimethylcyclopentadienyl)hafnium dichloride,diphenylsilylbis(2,3-dimethylcyclopentadienyl)hafnium dimethyl,methylphenylsilylbis(2,3-dimethylcyclopentadienyl)hafnium dichloride,methylphenylsilylbis(2,3-dimethylcyclopentadienyl)hafnium dimethyl,ethylenebis(2,3-dimethylcyclopentadienyl)hafnium dichloride,ethylenebis(2,3-dimethylcyclopentadienyl)hafnium dimethyl,methylenebis(2,3-dimethylcyclopentadienyl)hafnium dichloride,methylenebis(2,3-dimethylcyclopentadienyl)hafnium dimethyl,dimethylsilylbis(3-trimethylsilylcyclopentadienyl)zirconium dichloride,dimethylsilylbis(3-trimethylsilylcyclopentadienyl)zirconium dimethyl,diphenylsilylbis(3-trimethylsilylcyclopentadienyl)zirconium dichloride,diphenylsilylbis(3-trimethylsilylcyclopentadienyl)zirconium dimethyl,methylphenylsilylbis(3-trimethylsilylcyclopentadienyl)zirconiumdichloride,methylphenylsilylbis(3-trimethylsilylcyclopentadienyl)zirconiumdimethyl, ethylenebis(3-trimethylsilylcyclopentadienyl)zirconiumdichloride, ethylenebis(3-trimethylsilylcyclopentadienyl)zirconiumdimethyl, methylenebis(3-trimethylsilylcyclopentadienyl)zirconiumdichloride, methylenebis(3-trimethylsilylcyclopentadienyl)zirconiumdimethyl, dimethylsilylbis(3-trimethylsilylcyclopentadienyl)hafniumdichloride, dimethylsilylbis(3-trimethylsilylcyclopentadienyl)hafniumdimethyl, diphenylsilylbis(3-trimethylsilylcyclopentadienyl)hafniumdichloride, diphenylsilylbis(3-trimethylsilylcyclopentadienyl)hafniumdimethyl, methylphenylsilylbis(3-trimethylsilylcyclopentadienyl)hafniumdichloride,methylphenylsilylbis(3-trimethylsilylcyclopentadienyl)hafnium dimethyl,ethylenebis(3-trimethylsilylcyclopentadienyl)hafnium dichloride,ethylenebis(3-trimethylsilylcyclopentadienyl)hafnium dimethyl,methylenebis(3-trimethylsilylcyclopentadienyl)hafnium dichloride,methylenebis(3-trimethylsilylcyclopentadienyl)hafnium dimethyl,

[0376] dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0377] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0378] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0379] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0380] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0381] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0382] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0383] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0384] dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0385] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0386] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0387] dimethylsiladiyl(2-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0388] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0389] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0390] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0391] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0392] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0393] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0394] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0395] 9-silafluorendiyl(2-tert-butyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0396] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0397] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0398] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0399] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0400] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0401] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0402] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0403] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

[0404] dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0405] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0406] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0407] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0408] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0409] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0410] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0411] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0412] dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0413] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0414] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyldimethylsiladiyl(2-iso-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl;

[0415] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0416] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0417] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0418] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0419] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0420] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0421] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0422] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0423] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0424] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0425] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0426] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0427] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0428] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0429] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0430] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0431] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0432] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0433] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0434] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

[0435] dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0436] dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0437] dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0438] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0439] dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0440] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0441] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0442] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0443] dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0444] dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0445] dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0446] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0447] dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0448] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0449] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0450] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0451] 9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0452] dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0453] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0454] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0455] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0456] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0457] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0458] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0459] 9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0460] 9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0461] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dichloride;

[0462] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dichloride;

[0463] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0464] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0465] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0466] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

[0467] dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0468] dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0469] dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0470] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0471] dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0472] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0473] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0474] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0475] dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0476] dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0477] dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0478] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0479] dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0480] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0481] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0482] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0483] 9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0484] dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0485] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0486] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0487] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0488] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0489] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0490] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0491] 9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0492] 9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0493] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dimethyl;

[0494] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dimethyl;

[0495] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0496] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0497] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0498] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

[0499] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0500] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloridedimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0501] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0502] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0503] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0504] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0505] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0506] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0507] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0508] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0509] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0510] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0511] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0512] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0513] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0514] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0515] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0516] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0517] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0518] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0519] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0520] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0521] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0522] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0523] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0524] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0525] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

[0526] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0527] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyldimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0528] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0529] dimethylsiladiyl(2-isobutyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0530] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0531] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0532] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0533] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0534] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0535] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0536] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0537] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0538] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0539] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0540] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0541] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0542] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0543] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0544] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0545] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0546] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0547] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0548] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0549] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0550] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0551] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0552] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

[0553] dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0554] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0555] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0556] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0557] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0558] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0559] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0560] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0561] dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0562] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0563] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0564] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0565] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0566] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0567] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0568] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0569] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0570] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0571] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0572] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0573] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0574] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0575] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0576] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0577] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0578] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0579] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0580] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0581] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0582] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0583] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0584] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0585] dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0586] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0587] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0588] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0589] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0590] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0591] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0592] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0593] dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0594] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0595] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0596] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0597] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0598] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0599] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0600] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0601] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0602] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0603] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0604] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0605] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0606] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0607] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0608] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0609] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0610] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

[0611] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0612] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0613] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0614] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0615] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0616] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

[0617] dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0618] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0619] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0620] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0621] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0622] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0623] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0624] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0625] dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0626] dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0627] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0628] dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0629] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0630] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0631] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0632] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0633] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0634] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0635] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0636] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0637] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0638] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0639] dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0640] dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0641] dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0642] dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0643] dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0644] dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0645] dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0646] dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0647] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0648] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0649] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0650] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0651] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0652] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0653] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0654] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0655] 9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0656] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0657] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0658] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0659] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0660] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0661] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0662] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0663] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0664] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl) 4η⁴-1,4-diphenyl-1,3-butadiene;

[0665] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0666] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0667] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0668] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0669] 9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0670] 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0671] 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0672] 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0673] 9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0674] 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0675] 9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0676] 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0677] dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0678] dimethylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0679] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0680] dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0681] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0682] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0683] dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0684] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0685] dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0686] dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0687] dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0688] dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0689] dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0690] dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0691] dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0692] dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0693] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloridedimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0694] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0695] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0696] dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0697] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0698] dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0699] dimethylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0700] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0701] dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0702] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0703] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0704] dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0705] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0706] dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0707] dimethylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0708] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0709] dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0710] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0711] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0712] dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0713] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0714] dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0715] dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0716] dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0717] dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0718] dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0719] dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0720] dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0721] dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0722] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0723] dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl) 41,4-diphenyl-1,3-butadiene;

[0724] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0725] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0726] dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0727] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0728] dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0729] dimethylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0730] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0731] dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0732] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0733] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0734] dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0735] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0736] dimethylamidoborane(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0737] dimethylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0738] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0739] dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0740] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0741] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0742] dimethylamidoborane(2-sec-butyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0743] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0744] dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0745] dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0746] dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0747] dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0748] dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0749] dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0750] dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0751] dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0752] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl

[0753] dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0754] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0755] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0756] dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0757] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0758] dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0759] dimethylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0760] dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0761] dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0762] dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0763] dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0764] dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0765] dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0766] diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0767] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0768] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0769] diisopropylamidoborane(2-iso-propyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0770] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0771] diisopropylamidoborane(2-iso-butyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0772] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0773] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0774] diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0775] diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0776] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0777] diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0778] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0779] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0780] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0781] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0782] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride

[0783] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0784] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0785] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0786] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0787] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0788] diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0789] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0790] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0791] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0792] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0793] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0794] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0795] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0796] diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0797] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0798] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂, 4η⁴-1,4-diphenyl-1,3-butadiene;

[0799] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0800] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0801] diisopropylamidoborane(2-iso-butyl,4-[3,5-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0802] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0803] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0804] diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0805] diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0806] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0807] diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0808] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0809] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0810] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0811] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0812] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0813] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)η⁴-1,4-diphenyl-1,3-butadiene;

[0814] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0815] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0816] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0817] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0818] diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0819] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0820] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0821] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0822] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0823] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0824] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0825] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0826] diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0827] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0828] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0829] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0830] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0831] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0832] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0833] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0834] diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0835] diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0836] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0837] diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0838] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0839] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0840] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0841] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0842] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyldiisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0843] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0844] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0845] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0846] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0847] diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0848] diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0849] diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0850] diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0851] diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0852] diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0853] diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0854] diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0855] bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0856] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0857] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0858] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0859] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0860] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0861] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0862] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

[0863] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0864] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0865] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0866] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0867] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0868] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0869] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

[0870] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0871] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloridebis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0872] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0873] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0874] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0875] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

[0876] bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0877] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0878] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0879] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0880] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0881] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0882] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0883] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

[0884] bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0885] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0886] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0887] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0888] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0889] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0890] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂ 72 ⁴-1,4-diphenyl-1,3-butadiene;

[0891] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0892] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0893] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0894] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0895] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0896] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0897] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0898] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0899] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0900] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl) 2η⁴-1,4-diphenyl-1,3-butadiene;

[0901] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl) η⁴-1,4-diphenyl-1,3-butadiene;

[0902] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

[0903] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

[0904] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

[0905] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

[0906] bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η₄-1,4-diphenyl-1,3-butadiene;

[0907] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0908] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0909] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0910] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0911] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0912] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂ 1′-1,4-diphenyl-1,3-butadiene;

[0913] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

[0914] bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0915] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0916] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0917] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0918] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0919] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0920] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0921] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

[0922] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0923] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0924] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0925] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0926] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0927] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0928] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

[0929] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0930] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethylbis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0931] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0932] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0933] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0934] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

[0935] bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0936] bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0937] bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0938] bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0939] bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0940] bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

[0941] bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl; and

[0942] bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl; and the like.

[0943] The most preferred species are the racemic versions of:

[0944] dimethylsilylbis(indenyl)zirconium dichloride,dimethylsilylbis(indenyl) zirconium dimethyl,ethylenebis(indenyl)zirconium dichloride,

[0945] ethylenebis(indenyl)zirconium dimethyl,dimethylsilylbis(tetrahydorindenyl) zirconium dichloride,dimethylsilylbis(tetrahydorindenyl)zirconium dimethyl,

[0946] ethylenebis(tetrahydorindenyl)zirconium dichloride,ethylenebis(tetrahydorindenyl)zirconium dimethyl,dimethylsilylbis(2-methylindenyl)zirconium dichloride,dimethylsilylbis(2-methylindenyl) zirconium dimethyl,ethylenebis(2-methylindenyl)zirconium dichloride,

[0947] ethylenebis(2-methylindenyl)zirconium dimethyl,dimethylsilylbis(2-methyl-4 phenylindenyl)zirconium dichloride,dimethylsilylbis(2-methyl-4-phenylindenyl) zirconium dimethyl,ethylenebis(2-methyl-4-phenylindenyl)zirconium dichloride,

[0948] ethylenebis(2-methyl-4-phenylindenyl)zirconium dimethyl,dimethylsilylbis(4,7-dimethylindenyl)zirconium dichloride,dimethylsilylbis(4,7-dimethylindenyl) zirconium dimethyl,ethylenebis(4,7-dimethylindenyl)zirconium dichloride,

[0949] ethylenebis(4,7-dimethylindenyl)zirconium dimethyl,dimethylsilylbis(indenyl) hafnium dichloride,dimethylsilylbis(indenyl)hafnium dimethyl,

[0950] ethylenebis(indenyl)hafnium dichloride,ethylenebis(indenyl)hafnium dimethyl,

[0951] dimethylsilylbis(tetrahydorindenyl)hafnium dichloride,

[0952] dimethylsilylbis(tetrahydorindenyl)hafnium dimethyl,

[0953] ethylenebis(tetrahydorindenyl)hafnium dichloride,ethylenebis(tetrahydorindenyl) hafnium dimethyl,dimethylsilylbis(2-methylindenyl)hafnium dichloride,

[0954] dimethylsilylbis(2-methylindenyl)hafnium dimethyl,ethylenebis(2-methylindenyl)hafnium dichloride,ethylenebis(2-methylindenyl)hafnium dimethyl,dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride,

[0955] dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dimethyl,ethylenebis(2-methyl-4-phenylindenyl)hafnium dichloride,ethylenebis(2-methyl-4-phenylindenyl)hafnium dimethyl,dimethylsilylbis(4,7-dimethylindenyl)hafnium dichloride,dimethylsilylbis(4,7-dimethylindenyl)hafnium dimethyl,

[0956] ethylenebis(4,7-dimethylindenyl)hafnium dichloride, andethylenebis(4,7-dimethylindenyl)hafnium dimethyl.

[0957] Similarly, metallocene precursors providing tacticity controlexist where (A-Cp) is (Cp) (Cp*), both Cp and Cp* having substituents onthe cyclopentadienyl rings of sufficient steric bulk to restrictrotation of the cyclopentadienyl ligands such that the aforementionedsymmetry conditions are satisfied. Preferable chiral racemicmetallocenes of this type includebis(tricyclo[5.2.1.0^(2,6)]deca-2,5-dienyl)zirconium and -hafniumdimethyl,bis((1R)-9,9-dimethyltricyclo[6.1.1.0^(2,6)]deca-2,5-dienyl)zirconiumdimethyl, bis(tricyclo[5.2.1.0^(2,6)]deca-2,5,8-trienyl)zirconiumdimethyl, bis(tricyclo[5.2.2.0^(2,6)]undeca-2,5,8-trienyl)zirconium and-hafnium dimethyl andbis((1R,8R)-7,7,9,9-tetramethyl[6.1.0.1.0^(2,6)]deca-2,5-dienyl)zirconiumand -hafnium dimethyl.

[0958] Preferably metallocene precursors for the production ofpoly-alpha -olefins having enhanced syndiotactic character are alsothose of Equation 17 where S″ are independently chosen such that the twoCp-ligands have substantially different steric bulk. In order to producea syndiotactic polymer the pattern of the groups substituted on theCp-rings is important. Thus, by steric difference or stericallydifferent as used herein, it is intended to imply a difference betweenthe steric characteristics of the Cp and Cp* rings that renders each tobe symmetrical With respect to the A bridging group but different withrespect to each other that controls the approach of each successivemonomer unit that is added to the polymer chain. The steric differencebetween the Cp and Cp* rings act to block the approaching monomer from arandom approach such that the monomer is added to the polymer chain inthe syndiotactic configuration.

[0959] Preferable metallocene precursors for the production ofsyndiotactic polymers are those of Equation 17 where S″ areindependently chosen such that 1) the steric difference between the twoCp-ligands is maximized and 2) there remains a plane of symmetry throughthe metal center and the C₁ and C₁, carbon atoms of the Cp-rings inEquation 17. Thus, complexes such as Me₂C(□⁵-C₅H₄)(1-fluorenyl)MMe₂(where M=Ti, Zr, or Hf) which possess this symmetry are preferred, andgenerally produce the syndiotactic polymer with higher degrees ofstereoregularity than similar, but less symmetric, systems.Additionally, in the above equation, 1-fluorenyl may be substituted with3,8-di-t-butylfluorenyl, octahydrofluorenyl or3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,10,10,11,11-octahydrodibenzo[b,h]fluorene.Because pre-catalysts of this type often lose there ability to controlthe stereoregularity of the polymer under high temperature reactionconditions, to insure higher crystallinity in the material requiresusing these catalysts at lower reactor temperatures, preferably attemperatures below 80° C.

[0960] Preferred catalysts that can produce the lower molecular weightisotactic polypropylene are those described in U.S. Pat. No. 5,120,867,which is incorporated by reference herein. Any mixture of catalysts,including supported catalysts, which can be used together in a singlereactor or in a series reactor configuration, that can also produce thedesired polypropylene can be utilized in this invention to produce thein situ blend. Preferred catalysts include cyclopentadienyl transitionmetals compounds and derivatives thereof used in conjunction with analumoxane and/or a compatible non-coordinating anion.

[0961] Additional preferred catalysts that produce crystallinepolypropylene are discussed in Chem. rev. 2000, 100, 1253-1345, which isincorporated by reference herein.

[0962] The preferred choice of transition metal component for theamorphous polymer fraction is the mono-cyclopentadienyl transition metalcomponent of equation 10 where y is equal to 1. This preferred componentis illustrated in equation 18:

[0963] where A′, J, S′, X₁, X₂, L′, z and w as are previously definedand M is titanium. Substituent S″_(v) is defined to be the same as S″ inequation 10 where the subscript “v” denotes the carbon atom on thecyclopentadienyl ring to which the substituent is bonded and where therecan be zero, two or four substituents, S″, on the cyclopentadienyl ringprovided that the cyclopentadienyl ring is symmetrically substituted.Symmetrically substituted is defined to mean that the cyclopentadienylring is substituted in the 2 and 5 positions and/or 3 and 4 positionswith S″ groups that are of approximately of the same steric bulk.Typically the size of these S″ groups are within 2 carbons of eachother. Thus a cyclopentadienyl substituted at the 2 and the 5 positionswith methyl and ethyl respectively, or substituted at the 3 and the 4positions with hexyl and octyl, respectively, would be consideredsymmetric. Likewise, the cyclopentadienyl ring may be substituted at allfour sites with S″ groups and be considered symmetric as long as each ofthe symmetrical pairs are of similar steric bulk. Additionally, twoadjacent S″-groups in the 3 and 4 position may be linked to form a ringprovided that the new ring is also symmetrically substituted.

[0964] Catalyst systems of this type are known to impart 2,1-mistakeswhen incorporating C3 and higher alpha-olefins. The pre-catalysts whereS′ is bonded to the nitrogen ligand (J) via a 3° carbon (for examplewhen S′ is tert-butyl or 1-adamantyl) have fewer 2,1-mistakes then whenS′ is bonded to the nitrogen ligand (J) via a 1° carbon (for examplewhen S′ is n-butyl, methyl, or benzyl) or 2° carbon (for example when S′is cyclododecyl, cyclohexyl, or sec-butyl). The 2,1-mistakes in thepolymer backbone impart (CH₂)₂ units that can be beneficial to thepolymer properties. Polymers of this type, the characterization of suchpolymers and the catalyst systems used to produce such polymers aredescribed in U.S. Pat. No. 5,723,560 and is incorporated herein byreference. Lower Mw versions of such polymers can be produced bychanging process condition, for example, by increasing reactortemperature.

[0965] Preferred mono-cyclopentadienyl transition metal compounds which,according to the present invention, provide catalyst systems which arespecific to the production of atactic poly- alpha-olefins include:

[0966] dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido) titaniumdichloride, dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido) titaniumdichloride, dimethylsilyl(tetramethylcyclopentadienyl)(s-butylamido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(n-butylamido) titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,

[0967] diethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride,diethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido) titaniumdichloride, diethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dichloride,diethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdichloride, diethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride,methylene(tetramethylcyclopentadienyl)(cyclododecylamido) titaniumdichloride, methylene(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,

[0968] methylene(tetramethylcyclopentadienyl)(cyclohexylamido) titaniumdichloride,

[0969] methylene(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdichloride,

[0970] methylene(tetramethylcyclopentadienyl)(t-butylamido) titaniumdichloride,

[0971] ethylene(tetramethylcyclopentadienyl)(cyclododecylamido) titaniumdichloride,

[0972] ethylene(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,ethylene(tetramethylcyclopentadienyl)(cyclohexylamido) titaniumdichloride, ethylene(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dichloride, ethylene(tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(s-butylamido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(n-butylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,

[0973] diethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,

[0974] diethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,diethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido) titaniumdimethyl, diethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,diethylsilyl(tetramethylcyclopentadienyl)(t-butylamido) titaniumdimethyl, methylene(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,methylene(tetramethylcyclopentadienyl)(exo-2-norbornylamido) titaniumdimethyl, methylene(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,methylene(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdimethyl, methylene(tetramethylcyclopentadienyl)(t-butylamido) titaniumdimethyl, ethylene(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,ethylene(tetramethylcyclopentadienyl)(exo-2-norbornylamido) titaniumdimethyl, ethylene(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,ethylene(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdimethyl, ethylene(tetramethylcyclopentadienyl)(t-butylamido) titaniumdimethyl, dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclododecylamido)titanium dichloride,dimethylsilyl(2,5-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclohexylamido) titaniumdichloride,

[0975] dimethylsilyl(2,5-dimethylcyclopentadienyl)(1-adamantylamido)titanium dichloride,dimethylsilyl(2,5-dimethylcyclopentadienyl)(t-butylamido) titaniumdichloride,dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclododecylamido) titaniumdichloride,dimethylsilyl(3,4-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclohexylamido) titaniumdichloride,

[0976] dimethylsilyl(3,4-dimethylcyclopentadienyl)(1-adamantylamido)titanium dichloride,dimethylsilyl(3,4-dimethylcyclopentadienyl)(t-butylamido) titaniumdichloride,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclododecylamido)titanium dichloride,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclohexylamido)titanium dichloride,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(1-adamantylamido)titanium dichloride,

[0977] dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(t-butylamido)titanium dichloride,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclododecylamido)titanium dichloride,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclohexylamido)titanium dichloride,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(1-adamantylamido)titanium dichloride,

[0978] dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(t-butylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclododecylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclohexylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(1-adamantylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(t-butylamido)titanium dichloride,dimethylsilyl(2-tetrahydroindenyl)(cyclododecylamido) titaniumdichloride, dimethylsilyl(2-tetrahydroindenyl)(exo-2-norbornylamido)titanium dichloride, dimethylsilyl(2-tetrahydroindenyl)(cyclohexylamido)titanium dichloride,dimethylsilyl(2-tetrahydroindenyl)(1-adamantylamido) titaniumdichloride, dimethylsilyl(2-tetrahydroindenyl)(t-butylamido) titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclododecylamido) titaniumdimethyl,

[0979] dimethylsilyl(2,5-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclohexylamido) titaniumdimethyl, dimethylsilyl(2,5-dimethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(2,5-dimethylcyclopentadienyl)(t-butylamido) titaniumdimethyl, dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,

[0980] dimethylsilyl(3,4-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclohexylamido) titaniumdimethyl, dimethylsilyl(3,4-dimethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(3,4-dimethylcyclopentadienyl)(t-butylamido) titaniumdimethyl,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,

[0981] dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(t-butylamido) titaniumdimethyl,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,

[0982] dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(t-butylamido) titaniumdimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(t-butylamido)titanium dimethyl, dimethylsilyl(2-tetrahydroindenyl)(cyclododecylamido)titanium dimethyl,dimethylsilyl(2-tetrahydroindenyl)(exo-2-norbornylamido) titaniumdimethyl, dimethylsilyl(2-tetrahydroindenyl)(cyclohexylamido) titaniumdimethyl, dimethylsilyl(2-tetrahydroindenyl)(1-adamantylamido) titaniumdimethyl, dimethylsilyl(2-tetrahydroindenyl)(t-butylamido) titaniumdimethyl and the like.

[0983] The most preferred species are:

[0984] dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido) titaniumdichloride, dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,

[0985] dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdimethyl, anddimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl.

[0986] Additionally, at higher reaction temperatures, some catalyststhat produce syndiotactic poly- alpha-olefin at lower temperatures, willproduce virtually non-crystalline poly- alpha-olefins at highertemperatures. The choice of transition metal component for thisamorphous polymer fraction is a subset of the transition metal componentof equations 8-9. Preferred components of this type are illustrated inequation 19:

[0987] wherein A′, M, X₁ and X₂ are as previously defined. SubstituentsS″_(v) and S′″_(v) are independently defined as S″ in equations 8-9where the subscript “v” denotes the carbon atom on the Cp-ring orFlu-ring (fluorenyl-ring) to which the substituent is bonded.

[0988] Preferably metallocene precursors for producingpoly-alpha-olefins having largely amorphous character (when used ascatalysts under higher reactor temperature conditions) are those ofEquation 19 where S′″_(v) are independently chosen such that themetallocene framework has a plane of symmetry containing the metalcenter and bisecting the Flu- and Cp-rings. The A′ ligand need not besymmetrical—for example dimethylsilyl or methylphenylsilyl will noteffect the stereochemisty of the polymer produced. Substituent S′″_(v)is defined to be the same as S″ in equation 8-9 where the subscript “v”denotes the carbon atom on the cyclopentadienyl ring to which thesubstituent is bonded and where there can be zero, two or foursubstituents, S′″, on the cyclopentadienyl ring provided that thecyclopentadienyl ring is symmetrically substituted. Symmetricallysubstituted is defined to mean that the cyclopentadienyl ring issubstituted in the 2 and 5 positions and/or 3 and 4 positions with S′″groups that are of approximately of the same steric bulk. Typically thesize of these S′″ groups are within 2 carbons of each other. Thus acyclopentadienyl substituted at the 2 and the 5 positions with methyland ethyl respectively, or substituted at the 3 and the 4 positions withhexyl and octyl, respectively, would be considered symmetric. Likewise,the cyclopentadienyl ring may be substituted at all four sites with S′″groups and be considered symmetric as long as each of the symmetricalpairs are of similar steric bulk. Additionally, two adjacent S′″-groupsin the 3 and 4 position may be linked to form a ring provided that thenew ring is also symmetrically substituted. Because of the distantplacement of the S″_(v) substituents on the fluorenyl ring, thesesubstitutents need not be symmetrically placed on the fluorenyl ring.Hence, the fluorenyl ring may be substituted with form 0-7 substituentsthat may be the same or different. Two or more adjacent S″-groups mayoptionally be linked to form a ring.

[0989] Preferred metallocene transition metal compounds which, accordingto the present invention, provide catalyst systems which are specific tothe production of amorphous or low crystallinity poly- alpha-olefinsinclude:

[0990] isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

[0991] isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dimethyl,

[0992] methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

[0993] methylene(cyclopentadienyl)(fluorenyl)zirconium dimethyl,

[0994] diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconiumdichloride,

[0995] diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dimethyl,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconiumdichloride,

[0996]di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconiumdimethyl,di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconiumdimethyl, diphenylsilyl(cyclopentadienyl)(fluorenyl)zirconiumdichloride,

[0997] diphenylsilyl(cyclopentadienyl)(fluorenyl)zirconium dimethyl,

[0998] dimethylsilyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,

[0999] dimethylsilyl(cyclopentadienyl)(fluorenyl)zirconium dimethyl,

[1000] methylphenylsilyl(cyclopentadienyl)(fluorenyl)zirconiumdichloride,

[1001] methylphenylsilyl(cyclopentadienyl)(fluorenyl)zirconium dimethyl,

[1002] isopropylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

[1003] isopropylidene(cyclopentadienyl)(fluorenyl)hafnium dimethyl,

[1004] methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

[1005] methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl,

[1006] diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

[1007] diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(fluorenyl)hafniumdichloride,

[1008]di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(fluorenyl)hafniumdimethyl,di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(fluorenyl) hafniumdichloride,

[1009]di(p-trimethysilylphenyl)methylene(cyclopentadienyl)(fluorenyl)hafniumdimethyl, diphenylsilyl(cyclopentadienyl)(fluorenyl)hafnium dichloride,

[1010] diphenylsilyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,

[1011] dimethylsilyl(cyclopentadienyl)(fluorenyl)hafnium dichloride,

[1012] dimethylsilyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,

[1013] methylphenylsilyl(cyclopentadienyl)(fluorenyl)hafnium dichloride,

[1014] methylphenylsilyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,

[1015]isopropylidene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdichloride,

[1016]isopropylidene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdimethyl,

[1017] methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdichloride,

[1018] methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdimethyl,

[1019]diphenylmethylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconium

[1020] dichloride,diphenylmethylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl) zirconiumdimethyl,

[1021]di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconium dichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdimethyl,di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconium dichloride,di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdimethyl,diphenylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdichloride,diphenylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdimethyl,dimethylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdichloride,dimethylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdimethyl,methylphenylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdichloride,methylphenylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdimethyl,isopropylidene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdichloride,isopropylidene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl, methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdichloride, methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl,diphenylmethylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdichloride,diphenylmethylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl,di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafnium dichloride,di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl,diphenylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdichloride,diphenylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl,dimethylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdichloride,dimethylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl,methylphenylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdichloride,methylphenylsilyl(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl,

[1022]isopropylidene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,

[1023]isopropylidene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,

[1024]methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,

[1025]methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,

[1026]diphenylmethylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,

[1027]diphenylmethylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,

[1028]di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,

[1029]di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,

[1030]di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,

[1031]di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,

[1032]diphenylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,

[1033]diphenylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,

[1034]dimethylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,

[1035]dimethylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,

[1036]methylphenylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,

[1037]methylphenylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,

[1038]isopropylidene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,

[1039]isopropylidene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl,

[1040]methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,

[1041]methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl,

[1042]diphenylmethylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,

[1043]diphenylmethylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl,

[1044]di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,

[1045]di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl,

[1046]di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,

[1047]di(p-trimethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl,

[1048]diphenylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,

[1049]diphenylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl,

[1050]dimethylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,

[1051]dimethylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl,

[1052]methylphenylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,

[1053]methylphenylsilyl(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl, and the like.

[1054] The most preferred species are:di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconium dichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconium dimethyl,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl, anddi(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl.

[1055] Additionally, compounds of formula 20 may be used to produce theamorphous polymer fraction.

[1056] In this case, S″_(v) are independently chosen such that themetallocene framework has a plane of symmetry that bisects M and A′.Substituents S″_(v) are independently defined to be the same as S″ inequation 8-9 where the subscript “v” denotes the carbon atom on thecyclopentadienyl ring to which the substituent is bonded and where therecan be zero to four substituents, S″, on the cyclopentadienyl ringprovided that the cyclopentadienyl ring is symmetrically substituted.Symmetrically substituted is defined to mean that the cyclopentadienylring is substituted in the 2 and 2′ positions and/or 3 and 3′ positionsand/or 4 and 4′ positions and/or 5 and 5“positions with S″ groups thatare of approximately of the same steric bulk. Typically the size ofthese S″ groups are within 2 carbons of each other. Thus acyclopentadienyl substituted at the 2 and the 2′ positions with methyland ethyl respectively, or substituted at the 3 and the 3′ positionswith hexyl and octyl, respectively, would be considered symmetric.Likewise, the cyclopentadienyl ring may be substituted at all four siteswith S″ groups and be considered symmetric as long as each of thesymmetrical pairs are of similar steric bulk. Additionally, two adjacentS″-groups may be linked to form a ring provided that the new ring isalso symmetrically substituted. Such complexes such asmeso-Me₂Si(indenyl)₂ZrMe₂ meso-CH₂CH₂(indenyl)₂ZrCl₂ are well known inthe art and generally produce amorphous polymers useful in thisinvention.

[1057] Preferred meso-metallocene compounds which, according to thepresent invention, provide catalyst systems which are specific to theproduction of amorphous poly- alpha-olefins include the meso versionsof:

[1058] dimethylsilylbis(indenyl)zirconium dichloride,dimethylsilylbis(indenyl) zirconium dimethyl,diphenylsilylbis(indenyl)zirconium dichloride,

[1059] diphenylsilylbis(indenyl)zirconium dimethyl,methylphenylsilylbis(indenyl) zirconium dichloride,

[1060] methylphenylsilylbis(indenyl)zirconium dimethyl,ethylenebis(indenyl) zirconium dichloride, ethylenebis(indenyl)zirconiumdimethyl,

[1061] methylenebis(indenyl)zirconium dichloride,methylenebis(indenyl)zirconium dimethyl,dimethylsilylbis(indenyl)hafnium dichloride, dimethylsilylbis(indenyl)hafnium dimethyl, diphenylsilylbis(indenyl)hafnium dichloride,

[1062] diphenylsilylbis(indenyl)hafnium dimethyl,methylphenylsilylbis(indenyl) hafnium dichloride,methylphenylsilylbis(indenyl)hafnium dimethyl,

[1063] ethylenebis(indenyl)hafnium dichloride,ethylenebis(indenyl)hafnium dimethyl, methylenebis(indenyl)hafniumdichloride, methylenebis(indenyl)hafnium dimethyl,dimethylsilylbis(tetrahydroindenyl)zirconium dichloride,

[1064] dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[1065] diphenylsilylbis(tetrahydroindenyl)zirconium dichloride,

[1066] diphenylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[1067] methylphenylsilylbis(tetrahydroindenyl)zirconium dichloride,

[1068] methylphenylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[1069] ethylenebis(tetrahydroindenyl)zirconium dichloride,

[1070] ethylenebis(tetrahydroindenyl)zirconium dimethyl,

[1071] methylenebis(tetrahydroindenyl)zirconium dichloride,methylenebis(tetrahydroindenyl)zirconium dimethyl,

[1072] dimethylsilylbis(tetrahydroindenyl)hafnium dichloride,

[1073] dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[1074] diphenylsilylbis(tetrahydroindenyl)hafnium dichloride,

[1075] diphenylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[1076] methylphenylsilylbis(tetrahydroindenyl)hafnium dichloride,

[1077] methylphenylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[1078] ethylenebis(tetrahydroindenyl)hafnium dichloride,ethylenebis(tetrahydroindenyl) hafnium dimethyl,methylenebis(tetrahydroindenyl)hafnium dichloride,

[1079] methylenebis(tetrahydroindenyl)hafnium dimethyl,dimethylsilylbis(2-methylindenyl)zirconium dichloride,dimethylsilylbis(2-methylindenyl) zirconium dimethyl,diphenylsilylbis(2-methylindenyl)zirconium dichloride,

[1080] diphenylsilylbis(2-methylindenyl)zirconium dimethyl,methylphenylsilylbis(2-methylindenyl)zirconium dichloride,methylphenylsilylbis(2-methylindenyl) zirconium dimethyl,ethylenebis(2-methylindenyl)zirconium dichloride,

[1081] ethylenebis(2-methylindenyl)zirconium dimethyl,methylenebis(2-methylindenyl) zirconium dichloride,methylenebis(2-methylindenyl)zirconium dimethyl,

[1082] dimethylsilylbis(2-methylindenyl)hafnium dichloride,dimethylsilylbis(2-methylindenyl)hafnium dimethyl,diphenylsilylbis(2-methylindenyl)hafnium dichloride,diphenylsilylbis(2-methylindenyl)hafnium dimethyl,

[1083] methylphenylsilylbis(2-methylindenyl)hafnium dichloride,

[1084] methylphenylsilylbis(2-methylindenyl)hafnium dimethyl,ethylenebis(2-methylindenyl)hafnium dichloride,ethylenebis(2-methylindenyl)hafnium dimethyl,methylenebis(2-methylindenyl)hafnium dichloride,methylenebis(2-methylindenyl)hafnium dimethyl,dimethylsilylbis(2-methyl-4-phenylindenyl) zirconium dichloride,diphenylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,diphenylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride,

[1085] diphenylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,methylphenylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride,

[1086] methylphenylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,

[1087] ethylenebis(2-methyl-4-phenylindenyl)zirconium dichloride,ethylenebis(2-methyl-4-phenylindenyl)zirconium dimethyl,methylenebis(2-methyl-4-phenylindenyl)zirconium dichloride,methylenebis(2-methyl-4-phenylindenyl) zirconium dimethyl,dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride,dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dimethyl,

[1088] diphenylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride,diphenylsilylbis(2-methyl-4-phenylindenyl)hafnium dimethyl,

[1089] methylphenylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride,

[1090] methylphenylsilylbis(2-methyl-4-phenylindenyl)hafnium dimethyl,

[1091] ethylenebis(2-methyl-4-phenylindenyl)hafnium dichloride,ethylenebis(2-methyl-4-phenylindenyl)hafnium dimethyl,methylenebis(2-methyl-4-phenylindenyl) hafnium dichloride,methylenebis(2-methyl-4-phenylindenyl)hafnium dimethyl,

[1092] dimethylsilylbis(4,7-dimethylindenyl)zirconium dichloride,dimethylsilylbis(4,7-dimethylindenyl)zirconium dimethyl,diphenylsilylbis(4,7-dimethylindenyl) zirconium dichloride,diphenylsilylbis(4,7-dimethylindenyl)zirconium dimethyl,

[1093] methylphenylsilylbis(4,7-dimethylindenyl)zirconium dichloride,methylphenylsilylbis(4,7-dimethylindenyl)zirconium dimethyl,ethylenebis(4,7-dimethylindenyl)zirconium dichloride,ethylenebis(4,7-dimethylindenyl) zirconium dimethyl,methylenebis(4,7-dimethylindenyl)zirconium dichloride,

[1094] methylenebis(4,7-dimethylindenyl)zirconium dimethyl,dimethylsilylbis(4,7-dimethylindenyl)hafnium dichloride,dimethylsilylbis(4,7-dimethylindenyl) hafnium dimethyl,diphenylsilylbis(4,7-dimethylindenyl)hafnium dichloride,

[1095] diphenylsilylbis(4,7-dimethylindenyl)hafnium dimethyl,methylphenylsilylbis(4,7-dimethylindenyl)hafnium dichloride,

[1096] methylphenylsilylbis(4,7-dimethylindenyl)hafnium dimethyl,ethylenebis(4,7-dimethylindenyl)hafnium dichloride,ethylenebis(4,7-dimethylindenyl)hafnium dimethyl,methylenebis(4,7-dimethylindenyl)hafnium dichloride,

[1097] methylenebis(4,7-dimethylindenyl)hafnium dimethyl, and the like.

[1098] The most preferred species are the racemic versions of:

[1099] dimethylsilylbis(indenyl)zirconium dichloride,dimethylsilylbis(indenyl) zirconium dimethyl,ethylenebis(indenyl)zirconium dichloride,

[1100] ethylenebis(indenyl)zirconium dimethyl,dimethylsilylbis(indenyl)hafnium dichloride,dimethylsilylbis(indenyl)hafnium dimethyl, ethylenebis(indenyl) hafniumdichloride, ethylenebis(indenyl)hafnium dimethyl,

[1101] dimethylsilylbis(tetrahydroindenyl)zirconium dichloride,

[1102] dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[1103] ethylenebis(tetrahydroindenyl)zirconium dichloride,

[1104] ethylenebis(tetrahydroindenyl)zirconium dimethyl,

[1105] dimethylsilylbis(tetrahydroindenyl)hafnium dichloride,

[1106] dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[1107] ethylenebis(tetrahydroindenyl)hafnium dichloride,ethylenebis(tetrahydroindenyl) hafnium dimethyl,dimethylsilylbis(2-methylindenyl)zirconium dichloride,

[1108] dimethylsilylbis(2-methylindenyl)zirconium dimethyl,ethylenebis(2-methylindenyl)zirconium dichloride,ethylenebis(2-methylindenyl)zirconium dimethyl,dimethylsilylbis(2-methylindenyl)hafnium dichloride,

[1109] dimethylsilylbis(2-methylindenyl)hafnium dimethyl,ethylenebis(2-methylindenyl)hafnium dichloride, andethylenebis(2-methylindenyl)hafnium dimethyl

[1110] When two transition metal compound based catalysts are used inone reactor as a mixed catalyst system, the two transition metalcompounds should be chosen such that the two are compatible. A simplescreening method such as by ¹H or ¹³C NMR, known to those of ordinaryskill in the art, can be used to determine which transition metalcompounds are compatible.

[1111] It is preferable to use the same activator for the transitionmetal compounds, however, two different activators, such as anon-coordinating anion activator and an alumoxane, can be used incombination. If one or more transition metal compounds contain an X₁ orX₂ ligand which is not a hydride, hydrocarbyl, or substitutedhydrocarbyl, then the alumoxane should be contacted with the transitionmetal compounds prior to addition of the non-coordinating anionactivator.

[1112] Particularly preferred combinations of transition metal compoundsinclude:

[1113] (1) Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ (2-Me-4-PhInd=2-methyl-4-phenylindenyl,c-C₁₂H₂₃=cyclododecyl, Me₄C₅-tetramethylcyclopentadienyl) activated withan alumoxane, such as methylalumoxane or modified methylalumoxane;

[1114] (2) Me₂Si(Me₄C₅)(N-c-C, 2H₂₃)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1115] (3) Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂(2-MeInd=2-methyl-indenyl) activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1116] (4) Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1117] (5) Me₂Si(Me₄C₅)(N-1-adamantyl)TiCl₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1118] (6) Me₂Si(Me₄C₅)(N-1-adamantyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1119] (7) Me₂Si(Me₄C₅)(N-1-adamantyl)TiCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1120] (8) Me₂Si(Me₄C₅)(N-1-adamantyl)TiMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1121] (9) Me₂Si(Me₄C₅)(N-t-butyl)TiCl₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1122] (10) Me₂Si(Me₄C₅)(N-t-butyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1123] (11) Me₂Si(Me₄C₅)(N-t-butyl)TiCl₂ and rac-Me₂Si(2-MeInd)activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1124] (12) Me₂Si(Me₄C₅)(N-t-butyl)TiMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1125] (13) Me₂Si(Me₄C₅)(N-exo-norbornyl)TiCl₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1126] (14) Me₂Si(Me₄C₅)(N-exo-norbornyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1127] (15) Me₂Si(Me₄C₅)(N-exo-norbornyl)TiCl₂ andrac-Me₂Si(2-MeInd)₂ZrCl₂ activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1128] (16) Me₂Si(Me₄C₅)(N-exo-norbornyl)TiMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1129] (17) (p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfCl₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂(3,8-di-t-BuFlu=3,8-di-tert-butylfluorenyl, Cp=cyclopentadienyl)activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1130] (18) (p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1131] (19) (p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfCl₂ andrac-Me₂Si(2-MeInd)₂ZrCl₂ activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1132] (20) (p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1133] (21) meso-CH₂CH₂(Ind)₂ZrCl₂ and rac-Me₂Si(H₄Ind)₂ZrCl₂(Ind=indenyl, H₄Ind=tetrahydroindenyl) activated with an alumoxane, suchas methylalumoxane or modified methylalumoxane;

[1134] (22) meso-CH₂CH₂(Ind)₂ZrMe₂ and rac-Me₂Si(H₄Ind)₂ZrMe₂ activatedwith a non-coordinating anion activator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1135] (23) meso-CH₂CH₂(Ind)₂ZrCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1136] (24) meso-CH₂CH₂(Ind)₂ZrMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1137] (25) meso-Me₂Si(Ind)₂ZrCl₂ and rac-Me₂Si(H₄Ind)₂ZrCl₂ activatedwith an alumoxane, such as methylalumoxane or modified methylalumoxane;

[1138] (26) meso-Me₂Si(Ind)₂ZrMe₂ and rac-Me₂Si(H₄Ind)₂ZrMe₂ activatedwith a non-coordinating anion activator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1139] (27) meso-Me₂Si(Ind)₂ZrCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂ activatedwith an alumoxane, such as methylalumoxane or modified methylalumoxane;

[1140] (28) meso-Me₂Si(Ind)₂ZrMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activatedwith a non-coordinating anion activator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1141] (29) meso-Me₂Si(2-MeInd)₂ZrCl₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1142] (30) meso-Me₂Si(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1143] (31) meso-Me₂Si(2-MeInd)₂ZrCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1144] (32) meso-Me₂Si(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1145] (33) meso-CH₂CH₂(2-MeInd)₂ZrCl₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1146] (34) meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1147] (35) meso-CH₂CH₂(2-MeInd)₂ZrCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1148] (36) meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1149] (37) meso-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1150] (38) meso-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1151] (39) meso-CH₂CH₂(2-Me-4-PhInd)₂ZrCl₂ andrac-CH₂CH₂(2-Me-4-PhInd)₂ZrCl₂ activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1152] (40) meso-CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂ andrac-CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1153] (41) meso-CH₂CH₂(2-MeInd)₂ZrCl₂ and rac-CH₂CH₂(2-MePhInd)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1154] (42) meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-CH₂CH₂(2-MeInd)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1155] (43) meso-CH₂CH₂(Ind)₂ZrCl₂ and rac-CH₂CH₂(Ind)₂ZrCl₂ activatedwith an alumoxane, such as methylalumoxane or modified methylalumoxane;

[1156] (44) meso-CH₂CH₂(Ind)₂ZrMe₂ and rac-CH₂CH₂(Ind)₂ZrMe₂ activatedwith a non-coordinating anion activator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1157] (45) meso-Me₂Si(Ind)₂ZrCl₂ and rac-Me₂Si(Ind)₂ZrCl₂ activatedwith an alumoxane, such as methylalumoxane or modified methylalumoxane;

[1158] (46) meso-Me₂Si(Ind)₂ZrMe₂ and rac-Me₂Si(Ind)₂ZrMe₂ activatedwith a non-coordinating anion activator, such as N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron or triphenylcarboniumtetrakis(pentaflourophenyl)boron;

[1159] (47) meso-CH₂CH₂(Ind)₂ZrCl₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂(4,7-Me₂Ind=4,7-dimethylindenyl) activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1160] (48) meso-CH₂CH₂(Ind)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1161] (49) meso-Me₂Si(Ind)₂ZrCl₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane;

[1162] (50) meso-Me₂Si(Ind)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1163] (51) meso-CH₂CH₂(2-MeInd)₂ZrCl₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂(4,7-Me₂Ind=4,7-dimethylindenyl) activated with an alumoxane, such asmethylalumoxane or modified methylalumoxane;

[1164] (52) meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;

[1165] (53) meso-Me₂Si(2-MeInd)₂ZrCl₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂activated with an alumoxane, such as methylalumoxane or modifiedmethylalumoxane; and

[1166] (54) meso-Me₂Si(2-MeInd)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂activated with a non-coordinating anion activator, such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron ortriphenylcarbonium tetrakis(pentaflourophenyl)boron.

[1167] The two transition metal compounds (pre-catalysts) may be used inany ratio. Preferred molar ratios of (A) transition metal compound toproduce amorphous polymer to (B) transition metal compound to producecrystalline polymer fall within the range of (A:B) 1:1000 to 1000:1,alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively1:1 to 100:1, and alternatively 1:1 to 75:1, and alternatively 5:1 to50:1. The particular ratio chosen will depend on the exact pre-catalystschosen, the method of activation, and the end product desired. In aparticular embodiment, when using the two pre-catalysts (A-“amorphouspolymer producing precatalyst” and B-“crystalline polymer producingcatalyst”), where both are activated with the same activator, thepreferred mole percents, based upon the molecular weight of thepre-catalysts, are 10 to 99.9% A to 0.1 to 90% B, alternatively 25 to99% A to 0.5 to 50% B, alternatively 50 to 99% A to 1 to 25% B, andalternatively 75 to 99% A to 1 to 10% B.

[1168] In general the combined pre-catalyst compounds and the activatorare combined in ratios of about 1:10,000 to about 10:1. When alumoxaneor aluminum alkyl activators are used, the combinedpre-catalyst-to-activator molar ratio is from 1:5000 to 10:1,alternatively from 1:1000 to 10:1; alternatively, 1:500 to 2:1; or 1:300to 1:1. When ionizing activators are used, the combinedpre-catalyst-to-activator molar ratio is from 10:1 to 1:10; 5:1 to 1:5;2:1 to 1:2; or 1.2:1 to 1:1. Multiple activators may be used, includingusing mixes of alumoxanes or aluminum alkyls with ionizing activators.

[1169] In another preferred embodiment a third catalyst (pre-catalystplus activator) is present in the processes described above. The thirdcatalyst may be any of the pre-catalyst components listed herein.Preferred third pre-catalysts include those that are capable ofproducing waxes. Preferred examples include:

[1170] rac-dimethylsilylbis(4,7-dimethylindenyl)hafnium dichloride,rac-dimethylsilylbis(4,7-dimethylindenyl)hafnium dimethyl,rac-dimethylsilylbis(4,7-dimethylindenyl)zirconium dichloride,rac-dimethylsilylbis(4,7-dimethylindenyl) zirconium dimethyl,rac-dimethylsilylbis(indenyl)hafnium dichloride,rac-dimethylsilylbis(indenyl)hafnium dimethyl,rac-dimethylsilylbis(indenyl) zirconium dichloride,rac-dimethylsilylbis(indenyl)zirconium dimethyl,rac-dimethylsilylbis(tetrahydroindenyl)hafnium dichloride,rac-dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,rac-dimethylsilylbis(tetrahydroindenyl)zirconium dichloride,rac-dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl,rac-diphenylsilylbis(4,7-dimethylindenyl)hafnium dichloride,rac-diphenylsilylbis(4,7-dimethylindenyl) hafnium dimethyl,rac-diphenylsilylbis(4,7-dimethylindenyl)zirconium dichloride,rac-diphenylsilylbis(4,7-dimethylindenyl)zirconium dimethyl,rac-diphenylsilylbis(indenyl)hafnium dichloride,rac-diphenylsilylbis(indenyl) hafnium dimethyl,

[1171] rac-diphenylsilylbis(indenyl)zirconium dichloride,rac-diphenylsilylbis(indenyl) zirconium dimethyl,rac-diphenylsilylbis(tetrahydroindenyl)hafnium dichloride,

[1172] rac-diphenylsilylbis(tetrahydroindenyl)hafnium dimethyl,rac-diphenylsilylbis(tetrahydroindenyl)zirconium dichloride,rac-diphenylsilylbis(tetrahydroindenyl)zirconium dimethyl,rac-methylphenylsilylbis(4,7-dimethylindenyl)hafnium dichloride,rac-methylphenylsilylbis(4,7-dimethylindenyl)hafnium dimethyl,rac-methylphenylsilylbis(4,7-dimethylindenyl)zirconium dichloride,rac-methylphenylsilylbis(4,7-dimethylindenyl)zirconium dimethyl,rac-methylphenylsilylbis(indenyl)hafnium dichloride,rac-methylphenylsilylbis(indenyl)hafnium dimethyl,rac-methylphenylsilylbis(indenyl)zirconium dichloride,rac-methylphenylsilylbis(indenyl)zirconium dimethyl,rac-methylphenylsilylbis(tetrahydroindenyl)hafnium dichloride,rac-methylphenylsilylbis(tetrahydroindenyl)hafnium dimethyl,rac-methylphenylsilylbis(tetrahydroindenyl)zirconium dichloride,rac-methylphenylsilylbis(tetrahydroindenyl)zirconium dimethyl,rac-ethylenebis(4,7-dimethylindenyl)hafnium dichloride,rac-ethylenebis(4,7-dimethylindenyl) hafnium dimethyl,rac-ethylenebis(4,7-dimethylindenyl)zirconium dichloride,

[1173] rac-ethylenebis(4,7-dimethylindenyl)zirconium dimethyl,rac-ethylenebis(indenyl)hafnium dichloride,rac-ethylenebis(indenyl)hafnium dimethyl,rac-ethylenebis(indenyl)zirconium dichloride, rac-ethylenebis(indenyl)zirconium dimethyl, rac-ethylenebis(tetrahydroindenyl)hafniumdichloride, rac-ethylenebis(tetrahydroindenyl)hafnium dimethyl,rac-ethylenebis(tetrahydroindenyl)zirconium dichloride, and

[1174] rac-ethylenebis(tetrahydroindenyl)zirconium dimethyl

[1175] Three transition metal compounds (pre-catalysts) may be used inany ratio. Preferred molar ratios of (A) transition metal compound toproduce amorphous polypropylene to (B) transition metal compound toproduce crystalline polypropylene to (C) transition metal compound toproduce wax fall within the range of (A:B:C) 1:1000:500 to 1000:1:1,alternatively 1:100:50 to 500:1:1, alternatively 1:10:10 to 200:1:1,alternatively 1:1:1 to 100:1:50, and alternatively 1:1:10 to 75:1:50,and alternatively 5:1:1 to 50:1:50. The particular ratio chosen willdepend on the exact pre-catalysts chosen, the method of activation, andthe end product desired.

[1176] Additional preferred catalysts and process are described in U.S.Pat. Nos. 6,376,410 and 6,380,122, which are incorporated by referenceherein.

[1177] In another embodiment the catalyst compositions of this inventioninclude a support material or carrier. For example, the one or morecatalyst components and/or one or more activators may be deposited on,contacted with, vaporized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, one or more supports or carriers.

[1178] The support material is any of the conventional supportmaterials. Preferably the supported material is a porous supportmaterial, for example, talc, inorganic oxides and inorganic chlorides.Other support materials include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene polyolefins or polymeric compounds,zeolites, clays, or any other organic or inorganic support material andthe like, or mixtures thereof.

[1179] The preferred support materials are inorganic oxides that includethose Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supportsinclude silica, which may or may not be dehydrated, fumed silica,alumina (WO 99/60033), silica-alumina and mixtures thereof. Other usefulsupports include magnesia, titania, zirconia, magnesium chloride (U.S.Pat. No. 5,965,477), montmorillonite (European Patent EP-B 1 0 511 665),phyllosilicate, zeolites, talc, clays (U.S. Pat. No. 6,034,187) and thelike. Also, combinations of these support materials may be used, forexample, silica-chromium, silica-alumina, silica-titania and the like.Additional support materials may include those porous acrylic polymersdescribed in EP 0 767 184 B 1, which is incorporated herein byreference. Other support materials include nanocomposites as describedin PCT WO 99/47598, aerogels as described in WO 99/48605, spherulites asdescribed in U.S. Pat. No. 5,972,510 and polymeric beads as described inWO 99/50311, which are all herein incorporated by reference.

[1180] It is preferred that the support material, most preferably aninorganic oxide, has a surface area in the range of from about 10 toabout 700 m²/g, pore volume in the range of from about 0.1 to about 4.0cc/g and average particle size in the range of from about 5 to about 500μm. More preferably, the surface area of the support material is in therange of from about 50 to about 500 m²/g, pore volume of from about 0.5to about 3.5 cc/g and average particle size of from about 10 to about200 μm. Most preferably the surface area of the support material is inthe range is from about 1 00 to about 400 m²/g, pore volume from about0.8 to about 3.0 cc/g and average particle size is from about 5 to about100 μm. The average pore size of the carrier useful in the inventiontypically has pore size in the range of from 10 to 1000 Å, preferably 50to about 500 Å, and most preferably 75 to about 350A.

[1181] As is well known in the art, the catalysts may also be supportedtogether on one inert support, or the catalysts may be independentlyplaced on two inert supports and subsequently mixed. Of the two methods,the former is preferred.

[1182] In another embodiment the support may comprise one or more typesof support material which may be treated differently. For example onecould use tow different silicas that had different pore volumes or hadbeen calcined at different temperatures. Likewise one could use a silicathat had been treated with a scavenger or other additive and a silicathat had not.

[1183] The stereospecific catalysts may be used to prepare macromonomerhaving a Mw of 100,000 or less and a crystallinity of 30% or morepreferably having vinyl termini.

[1184] As a specific example, a method for preparing propylene-basedmacromonomers having a high percentage of vinyl terminal bonds involves:

[1185] a) contacting, in solution, propylene, optionally a minor amountof copolymerizable monomer, with a catalyst composition containing thestereorigid, activated transition metal catalyst compound at atemperature from about 80° C. to about 140° C.; and

[1186] b) recovering isotactic or syndiotactic polypropylene chainshaving number average molecular weights of about 2,000 to about 30,000Daltons.

[1187] Preferably, the solution comprises a hydrocarbon solvent. Morepreferably, the hydrocarbon solvent is aliphatic or aromatic. Also, thepropylene monomers are preferably contacted at a temperature from 90° C.to 120° C. More preferably, a temperature from 95° C. to 115° C. isused. Most preferably, the propylene monomers are contacted at atemperature from 100° C. to 110° C. Reactor pressure generally can varyfrom atmospheric to 345 MPa, preferably to 182 MPa. The reactions can berun in batch or in continuous mode. Conditions for suitable slurry-typereactions will also be suitable and are similar to solution conditions,the polymerization typically being run in liquid propylene underpressures suitable to such.

[1188] The catalyst pair selection criteria were discussed earlier. Onecatalyst typically is stereospecific with the ability to producesignificant population of vinyl-terminated macromonomers, the othertypically is a specific and capable of incorporating the reactivemacromonomers. In general it is believed that C2 symmetric bulky ligandmetallocene catalysts can produce vinyl terminated isotacticpolypropylene macromonomers. Catalysts that favor betamethyl-eliminationalso often appear to also favor isotactic polypropylene macromonomerformation. Rac-dimethylsilyl bis(indenyl)hafnium dimethyl, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, and rac-ethylenebis(4,7-dimethylindenyl)hafnium dimethyl are catalysts capable ofproducing isotactic polypropylene having high vinyl chain terminationfor use in this invention. High temperatures, typically above 80° C.,appear to positively influence vinyl termination. Likewise,Me₂Si(Me₄C₅)(N-c-C₂H₂₃)TiMe₂ and Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂ produceamorphous polypropylene useful in this invention and are believed toincorporate the vinyl terminated macromonomers to also produce a graftedstructure of scPP side chains on an amorphous backbone.

[1189] In alternate embodiments dienes such as 1,9-decadiene areintroduced into the reaction zone to promote the production ofvinyl-terminated aPP and scPP macromonomers that help increase thepopulation of branch-block species.

[1190] Polymerization Processes

[1191] The catalysts and catalyst systems described above are suitablefor use in a solution, bulk, gas or slurry polymerization process or acombination thereof, preferably solution phase or bulk phasepolymerization process.

[1192] In one embodiment, this invention is directed toward thesolution, bulk, slurry or gas phase polymerization reactions involvingthe polymerization of one or more of monomers having from 3 to 30 carbonatoms, preferably 3-12 carbon atoms, and more preferably 3 to 8 carbonatoms. Preferred monomers include one or more of propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1,decene-1,3-methyl-pentene-1, and cyclic olefins or a combinationthereof. Other monomers can include vinyl monomers, diolefins such asdienes, polyenes, norbornene, norbornadiene, vinyl norbornene,ethylidene norbornene monomers. Preferably a homopolymer or copolymer ofpropylene is produced. In another embodiment, both a homopolymer ofpropylene and a copolymer of propylene and one or more of the monomerslisted above are produced.

[1193] One or more reactors in series or in parallel may be used in thepresent invention. Catalyst component and activator may be delivered asa solution or slurry, either separately to the reactor, activatedin-line just prior to the reactor, or preactivated and pumped as anactivated solution or slurry to the reactor. A preferred operation istwo solutions activated in-line. For more information on methods tointroduce multiple catalysts into reactors, please see U.S. Pat. No.6,399,722, and WO0130862A1. While these references may emphasize gasphase reactors, the techniques described are equally applicable to othertypes of reactors, including continuous stirred tank reactors, slurryloop reactors and the like. Polymerizations are carried out in eithersingle reactor operation, in which monomer, comonomers,catalyst/activator, scavenger, and optional modifiers are addedcontinuously to a single reactor or in series reactor operation, inwhich the above components are added to each of two or more reactorsconnected in series. The catalyst components can be added to the firstreactor in the series. The catalyst component may also be added to bothreactors, with one component being added to first reaction and anothercomponent to other reactors.

[1194] In one embodiment 500 ppm or less of hydrogen is added to thepolymerization, or 400 ppm or less, or 300 ppm or less. In otherembodiments at least 50 ppm of hydrogen is added to the polymerization,or 100 ppm or more, or 150 ppm or more.

[1195] Gas Phase Polymerization

[1196] Generally, in a fluidized gas bed process used for producingpolymers, a gaseous stream containing one or more monomers iscontinuously cycled through a fluidized bed in the presence of acatalyst under reactive conditions. The gaseous stream is withdrawn fromthe fluidized bed and recycled back into the reactor. Simultaneously,polymer product is withdrawn from the reactor and fresh monomer is addedto replace the polymerized monomer. (See for example U.S. Pat. Nos.4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922,5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228 all of whichare fully incorporated herein by reference.)

[1197] Slurry Phase Polymerization

[1198] A slurry polymerization process generally operates between 1 toabout 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068kPa) or even greater and temperatures in the range of 0° C. to about120° C. In a slurry polymerization, a suspension of solid, particulatepolymer is formed in a liquid polymerization diluent medium to whichmonomer and comonomers along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[1199] In one embodiment, a preferred polymerization technique useful inthe invention is referred to as a particle form polymerization, or aslurry process where the temperature is kept below the temperature atwhich the polymer goes into solution. Such technique is well known inthe art, and described in for instance U.S. Pat. No. 3,248,179 which isfully incorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

[1200] In another embodiment, the slurry process is carried outcontinuously in a loop reactor. The catalyst, as a slurry in isobutaneor as a dry free flowing powder, is injected regularly to the reactorloop, which is itself filled with circulating slurry of growing polymerparticles in a diluent of isobutane containing monomer and comonomer.Hydrogen, optionally, may be added as a molecular weight control. (Inone embodiment 500 ppm or less of hydrogen is added, or 400 ppm or lessor 300 ppm or less. In other embodiments at least 50 ppm of hydrogen isadded, or 100 ppm or more, or 150 ppm or more.)

[1201] The reactor is maintained at a pressure of 3620 kPa to 4309 kPaand at a temperature in the range of about 60° C. to about 104° C.depending on the desired polymer melting characteristics. Reaction heatis removed through the loop wall since much of the reactor is in theform of a double-jacketed pipe. The slurry is allowed to exit thereactor at regular intervals or continuously to a heated low pressureflash vessel, rotary dryer and a nitrogen purge column in sequence forremoval of the isobutane diluent and all unreacted monomer andcomonomers. The resulting hydrocarbon free powder is then compounded foruse in various applications.

[1202] In another embodiment, the reactor used in the slurry processuseful in the invention is capable of and the process useful in theinvention is producing greater than 2000 lbs. of polymer per hour (907Kg/hr), more preferably greater than 5000 lb./hr (2268 Kg/hr), and mostpreferably greater than 10,000 lbs./hr (4540 Kg/hr). In anotherembodiment the slurry reactor used in the process useful in theinvention is producing greater than 15,000 lbs. of polymer per hour(6804 Kg/hr), preferably greater than 25,000 lbs./hr (11,340 Kg/hr) toabout 100,000 lbs./hr (45,500 Kg/hr).

[1203] In another embodiment in the slurry process useful in theinvention the total reactor pressure is in the range of from 400 psig(2758 kPa) to 800 psig (5516 kPa), preferably 450 psig (3103 kPa) toabout 700 psig (4827 kPa), more preferably 500 psig (3448 kPa) to about650 psig (4482 kPa), most preferably from about 525 psig (3620 kPa) to625 psig (4309 kPa).

[1204] In yet another embodiment in the slurry process useful in theinvention the concentration of predominant monomer in the reactor liquidmedium is in the range of from about 1 to 10 weight percent, preferablyfrom about 2 to about 7 weight percent, more preferably from about 2.5to about 6 weight percent, most preferably from about 3 to about 6weight percent.

[1205] Another process useful in the invention is where the process,preferably a slurry process is operated in the absence of or essentiallyfree of any scavengers, such as triethylaluminum, trimethylaluminum,tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This process is described in PCTpublication WO 96/08520 and U.S. Pat. No. 5,712,352, which are hereinfully incorporated by reference.

[1206] In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-isobutyl aluminum and anexcess of alumoxane or modified alumoxane.

[1207] Homogeneous, Bulk, or Solution Phase Polymerization

[1208] The catalysts described herein can be used advantageously inhomogeneous solution processes. Generally this involves polymerizationin a continuous reactor in which the polymer formed and the startingmonomer and catalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 to 3000 bar (10-30,000MPa), in which the monomer acts as diluent or in solution polymerizationusing a solvent.

[1209] Temperature control in the reactor is obtained by balancing theheat of polymerization with reactor cooling by reactor jackets orcooling coils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds may also be used. The reactor temperature depends onthe catalyst used. In general, the reactor temperature preferably canvary between about 30° C. and about 160° C., more preferably from about90° C. to about 150° C., and most preferably from about 100° C. to about140° C. Polymerization temperature may vary depending on catalystchoice. For example a diimine Ni catalyst may be used at 40° C., while ametallocene Ti catalyst can be used at 100° C. or more. In seriesoperation, the second reactor temperature is preferably higher than thefirst reactor temperature. In parallel reactor operation, thetemperatures of the two reactors are independent. The pressure can varyfrom about 1 mm Hg to 2500 bar (25,000 MPa), preferably from 0.1 bar to1600 bar (1-16,000 MPa), most preferably from 1.0 to 500 bar (10-5000MPa).

[1210] In one embodiment 500 ppm or less of hydrogen is added to thepolymerization, or 400 ppm or less or 300 ppm or less. In otherembodiments at least 50 ppm of hydrogen is added to the polymerization,or 100 ppm or more, or 150 ppm or more.

[1211] Each of these processes may also be employed in single reactor,parallel or series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the desired polymers. Hydrocarbon solventsare suitable, both aliphatic and aromatic. Alkanes, such as hexane,pentane, isopentane, and octane, are preferred.

[1212] The process can be carried out in a continuous stirred tankreactor, batch reactor or plug flow reactor, or more than one reactoroperated in series or parallel. These reactors may have or may not haveinternal cooling or heating and the monomer feed may or may not berefrigerated. See the general disclosure of U.S. Pat. No. 5,001,205 forgeneral process conditions. See also, international application WO96/33227 and WO 97/22639. All documents are incorporated by referencefor US purposes for description of polymerization processes, metalloceneselection and useful scavenging compounds.

[1213] This invention further relates to a continuous process to preparean adhesive comprising:

[1214] 1) combining monomer, optional solvent, catalyst and activator ina reactor system,

[1215] 2) withdrawing polymer solution from the reactor system,

[1216] 3) removing at least 10% solvent, if present, from the polymersolution,

[1217] 4) quenching the reaction,

[1218] 5) devolatilizing the polymer solution to form molten polymer,

[1219] 6) combining the molten polymer and one or more additives (suchas those described below) in a mixer, such as a static mixer, (in apreferred embodiment tackifier is not added or is added in amounts ofless than 30 weight %, preferably less than 20 weight %, more preferablyin amounts of less than 10 weight %),

[1220] 7) removing the polymer combination from the mixer, and

[1221] 8) pelletizing or drumming the polymer combination; where step 1)comprises any of the processes described above.

[1222] In another embodiment this invention relates to a continuousprocess to prepare an adhesive comprising:

[1223] 1) combining monomer, optional solvent, catalyst and activator ina reactor system,

[1224] 2) withdrawing polymer solution from the reactor system,

[1225] 3) removing at least 10% solvent, if present, from the polymersolution,

[1226] 4) quenching the reaction,

[1227] 5) devolatilizing the polymer solution to form molten polymer,

[1228] 6) combining the molten polymer and one or more additives in amixer, such as a static mixer,

[1229] 7) removing the polymer combination from the mixer, and

[1230] 8) pelletizing or drumming the polymer combination.

[1231] In a particularly preferred embodiment, this invention relates toa continuous process to make an adhesive comprising

[1232] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less and a crystallinity of 20% orless under selected polymerization conditions;

[1233] 2) selecting a second catalyst component capable of producingpolymer having an Mw of 100,000 or less and a crystallinity of 40% ormore at the selected polymerization conditions;

[1234] 3) contacting, in a solvent and in a reaction zone under theselected polymerization conditions, the catalyst components in thepresence of one or more activators with one or more C3 to C40 olefins,and, optionally one or more diolefins;

[1235] 4) at a temperature of greater than 100° C.;

[1236] 5) at a residence time of 120 minutes or less (preferably 60 to120 minutes);

[1237] 6) wherein the ratio of the first catalyst to the second catalystis from 1:1 to 50:1;

[1238] 7) wherein the activity of the catalyst components is at least 50kilograms of polymer per gram of the catalyst components; and wherein atleast 20% of the olefins are converted to polymer;

[1239] 8) withdrawing polymer solution from the reaction zone;

[1240] 9) removing at least 10% solvent from the polymer solution;

[1241] 10) quenching the reaction;

[1242] 11) devolatilizing the polymer solution to form molten polymer;

[1243] 12) combining the molten polymer and one or more additives in amixer, such as a static mixer;

[1244] 13) removing the polymer combination from the mixer; and

[1245] 14) pelletizing or drumming the polymer combination.

[1246] In a particularly preferred embodiment, this invention relates toa continuous process to make an adhesive comprising

[1247] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less and a crystallinity of 20% orless under selected polymerization conditions;

[1248] 2) selecting a second catalyst component capable of producingpolymer having an Mw of 100,000 or less and a crystallinity of 40% ormore at the selected polymerization conditions;

[1249] 3) contacting, in a solvent and in a reaction zone under theselected polymerization conditions, the catalyst components in thepresence of one or more activators with one or more C3 to C40 olefins,and, optionally one or more diolefins;

[1250] 4) at a temperature of greater than 100° C.;

[1251] 5) at a residence time of 120 minutes or less;

[1252] 6) wherein the ratio of the first catalyst to the second catalystis from 1:1 to 50:1;

[1253] 7) wherein the activity of the catalyst components is at least 50kilograms of polymer per gram of the catalyst components; and wherein atleast 50% of the olefins are converted to polymer;

[1254] 8) withdrawing polymer solution from the reaction zone;

[1255] 9) removing at least 10% solvent from the polymer solution;

[1256] 10) quenching the reaction;

[1257] 11) forming molten polymer where the polymer comprises one ormore C3 to C40 olefins, and less than 50 mole % of ethylene, and wherethe polymer has:

[1258] a) a Dot T-Peel of 1 Newton or more; and

[1259] b) a branching index (g′) of 0.95 or less measured at the Mz ofthe polymer; and

[1260] c) an Mw of 100,000 or less; and

[1261] 12) combining the molten polymer and one or more additives in amixer, such as a static mixer;

[1262] 13) removing the polymer combination from the mixer; and

[1263] 14) pelletizing or drumming the polymer combination.

[1264] In a particularly preferred embodiment, this invention relates toa continuous process to make an adhesive comprising

[1265] 1) selecting a first catalyst component capable of producing apolymer having an Mw of 100,000 or less and a crystallinity of 20% orless under selected polymerization conditions;

[1266] 2) selecting a second catalyst component capable of producingpolymer having an Mw of 100,000 or less and a crystallinity of 40% ormore at the selected polymerization conditions;

[1267] 3) contacting, in a solvent and in a reaction zone under theselected polymerization conditions, the catalyst components in thepresence of one or more activators with one or more C3 to C40 olefins,and, optionally one or more diolefins;

[1268] 4) at a temperature of greater than 100° C.;

[1269] 5) at a residence time of 120 minutes or less;

[1270] 6) wherein the ratio of the first catalyst to the second catalystis from 1:1 to 50:1;

[1271] 7) wherein the activity of the catalyst components is at least 50kilograms of polymer per gram of the catalyst components; and wherein atleast 50% of the olefins are converted to polymer;

[1272] 8) withdrawing polymer solution from the reaction zone;

[1273] 9) removing at least 10% solvent from the polymer solution;

[1274] 10) quenching the reaction;

[1275] 11) forming molten polymer where the polymer comprises one ormore C3 to C40 olefins (preferably propylene), and less than 50 mole %of ethylene, and where the polymer has:

[1276] a) a Dot T-Peel of 3 Newton or more; and

[1277] b) a branching index (g′) of 0.90 or less measured at the Mz ofthe polymer; and

[1278] c) an Mw of 30,000 or less;

[1279] d) a peak melting point between 60 and 190° C.,

[1280] e) a Heat of fusion of 1 to 70 J/g,

[1281] f) a melt viscosity of 8000 mPa·sec or less at 190° C.; and

[1282] 12) combining the molten polymer and one or more additives in amixer, such as a static mixer;

[1283] 13) removing the polymer combination from the mixer; and

[1284] 14) pelletizing or drumming the polymer combination.

[1285] In another embodiment this invention relates to a continuousprocess to prepare an adhesive comprising:

[1286] 1) combining monomer, catalyst and activator in a reactor system,

[1287] 2) withdrawing polymer from the reactor system,

[1288] 3) quenching the reaction,

[1289] 4) forming molten polymer,

[1290] 5) combining the molten polymer and one or more additives, and

[1291] 6) pelletizing or drumming the polymer combination.

[1292] Formulations of the Polymers

[1293] The polymers produced herein then can be used directly as anadhesive or blended with other components to form an adhesive.

[1294] Tackifiers are typically not needed with the polymers of thisinvention. However if tackifier is desired, the tackifiers that may beblended with the polymers described above are those typically used inthe art. Examples include, but are not limited to, aliphatic hydrocarbonresins, aromatic modified aliphatic hydrocarbon resins, hydrogenatedpolycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gumrosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oilrosin esters, polyterpenes, aromatic modified polyterpenes, terpenephenolics, aromatic modified hydrogenated polycyclopentadiene resins,hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins,hydrogenated terpenes and modified terpenes, and hydrogenated rosinesters. In some embodiments the tackifier is hydrogenated. In otherembodiments the tackifier is non-polar. (Non-polar meaning that thetackifier is substantially free of monomers having polar groups.Preferably the polar groups are not present, however if they arepreferably they are not present at more that 5 weight %, preferably notmore that 2 weight %, even more preferably no more than 0.5 weight %.)In some embodiments the tackifier has a softening point (Ring and Ball,as measured by ASTM E-28) of 80° C. to 150° C., preferably 100° C. to130° C.

[1295] The tackifier, if present, is typically present at about 1 weight% to about 80 weight %, based upon the weight of the blend, morepreferably 2 weight % to 40 weight %, even more preferably 3 weight % to30 weight %.

[1296] Preferred hydrocarbon resins for use as tackifiers or modifiersinclude:

[1297] 1. Resins such as C5/C6 terpene resins, styrene terpenes,alpha-methyl styrene terpene resins, C9 terpene resins, aromaticmodified C5/C6, aromatic modified cyclic resins, aromatic modifieddicyclopentadiene based resins or mixtures thereof. Additional preferredresins include those described in WO 91/07472, U.S. Pat. No. 5,571,867,U.S. Pat. No. 5,171,793 and U.S. Pat. No. 4,078,132. Typically theseresins are obtained from the cationic polymerization of compositionscontaining one or more of the following monomers: C5 diolefins (such as1-3 pentadiene, isoprene, etc); C5 olefins (such as 2-methylbutenes,cyclopentene, etc.); C6 olefins (such as hexene), C9 vinylaromatics(such as styrene, alpha methyl styrene, vinyltoluene, indene, methylindene, etc.); cyclics (such as dicyclopentadiene,methyldicyclopentadiene, etc.); and or terpenes (such as limonene,carene, etc).

[1298] 2. Resins obtained by the thermal polymerization ofdicyclopentadiene, and/or the thermal polymerization of dimers oroligomers of cyclopentadiene and/or methylcyclopentadiene, optionallywith vinylaromatics (such as styrene, alpha-methyl styrene, vinyltoluene, indene, methyl indene).

[1299] The resins obtained after polymerization and separation ofunreacted materials, can be hydrogenated if desired. Examples ofpreferred resins include those described in U.S. Pat. No. 4,078,132; WO91/07472; U.S. Pat. No. 4,994,516; EP 0 046 344 A; EP 0 082 726 A; andU.S. Pat. No. 5,171,793.

[1300] In another embodiment an adhesive composition comprising polymerproduct of this invention further comprises a crosslinking agent.Preferred crosslinking agents include those having functional groupsthat can react with the acid or anhydride group. Preferred crosslinkingagents include alcohols, multiols, amines, diamines and/or triamines.Examples of crosslinking agents useful in this invention includepolyamines such as ethylenediamine, diethylenetriamine,hexamethylenediamine, diethylaniinopropylamine, and/or menthanediamine.

[1301] In another embodiment an adhesive composition comprising thepolymer product of this invention further comprises typical additivesknown in the art such as fillers, antioxidants, adjuvants, adhesionpromoters, oils, and/or plasticizers. Preferred fillers include titaniumdioxide, calcium carbonate, barium sulfate, silica, silicon dioxide,carbon black, sand, glass beads, mineral aggregates, talc, clay and thelike. Preferred antioxidants include phenolic antioxidants, such asIrganox 1010, Irganox, 1076 both available from Ciba-Geigy. Preferredoils include paraffinic or napthenic oils such as Primol 3 52, or Primol876 available from ExxonMobil Chemical France, S.A. in Paris, France.Preferred plasticizers include polybutenes, such as Parapol 950 andParapol 1300 available from ExxonMobil Chemical Company in Houston Tex.Other preferred additives include block, antiblock, pigments, processingaids, UV stabilizers, neutralizers, lubricants, surfactants and/ornucleating agents may also be present in one or more than one layer inthe films. Preferred additives include silicon dioxide, titaniumdioxide, polydimethylsiloxane, talc, dyes, wax, calcium sterate, carbonblack, low molecular weight resins and glass beads. Preferred adhesionpromoters include polar acids, polyaminoamides (such as Versamid 115,125, 140, available from Henkel), urethanes (such as isocyanate/hydroxyterminated polyester systems, e.g. bonding agent TN/Mondur Cb-75(Miles,Inc.), coupling agents, (such as silane esters (Z-6020 from DowCorning)), titanate esters (such as Kr-44 available from Kenrich),reactive acrylate monomers (such as sarbox SB-600 from Sartomer), metalacid salts (such as Saret 633 from Sartomer), polyphenylene oxide,oxidized polyolefins, acid modified polyolefins, and anhydride modifiedpolyolefins.

[1302] In another embodiment the polymers of this invention are combinedwith less than 3 wt % anti-oxidant, less than 3 wt % flow improver, lessthan 10 wt % wax, and or less than 3 wt % crystallization aid.

[1303] Other optional components that may be combined with the polymerproduct of this invention are plasticizers or other additives such asoils, surfactants, fillers, color masterbatches, and the like. Preferredplasticizers include mineral oils, polybutenes, phthalates and the like.Particularly preferred plasticizers include phthalates such asdiisoundecyl phthalate (DIUP), diisononylphthalate (DINP),dioctylphthalates (DOP) and the like. Particularly preferred oilsinclude aliphatic naphthenic oils.

[1304] Other optional components that may be combined with the polymerproduct of this invention are low molecular weight products such as wax,oil or low Mn polymer, (low meaning below Mn of 5000, preferably below4000, more preferably below 3000, even more preferably below 2500).Preferred waxes include polar or non-polar waxes, functionalized waxes,polypropylene waxes, polyethylene waxes, and wax modifiers. Preferredwaxes include ESCOME™ 101. Preferred functionalized waxes include thosemodified with an alcohol, an acid, a ketone, an anhydride and the like.Preferred examples include waxes modified by methyl ketone, maleicanhydride or maleic acid. Preferred oils include aliphatic napthenicoils, white oils or the like. Preferred low Mn polymers include polymersof lower alpha olefins such as propylene, butene, pentene, hexene andthe like. A particularly preferred polymer includes polybutene having anMn of less than 1000. An example of such a polymer is available underthe trade name PARAPOL™ 950 from ExxonMobil Chemical Company. PARAPOL™950 is a liquid polybutene polymer having an Mn of 950 and a kinematicviscosity of 220 cSt at 100° C., as measured by ASTM D 445. In someembodiments the polar and non-polar waxes are used together in the samecomposition.

[1305] In some embodiments, however, wax may not be desired and ispresent at less than 5 weight %, preferably less than 3 weight %, morepreferably less than 1 weight %, more preferably less than 0.5 weight %,based upon the weight of the composition.

[1306] In another embodiment the polymers of this invention have lessthan 30 weight % total of any combination of additives described above,preferably less than 25 weight %, preferably less than 20 weight %,preferably less than 15 weight %, preferably less than 10 weight %,preferably less than 5 weight %, based upon the weight of the polymerand the additives.

[1307] In another embodiment the polymer produced by this invention maybe blended with elastomers (preferred elastomers include all natural andsynthetic rubbers, including those defined in ASTM D1566). In apreferred embodiment elastomers are blended with the polymer produced bythis invention to form rubber toughened compositions. In a particularlypreferred embodiment the rubber toughened composition is a two (or more)phase system where the rubber is a discontinuous phase and the polymeris a continuous phase. Examples of preferred elastomers include one ormore of the following: ethylene propylene rubber, ethylene propylenediene monomer rubber, neoprene rubber, styrenic block copolymer rubbers(including SI, SIS, SB, SBS, SIBS and the like), butyl rubber, halobutylrubber, copolymers of isobutylene and para-alkylstyrene, halogenatedcopolymers of isobutylene and para-alkylstyrene. This blend may becombined with the tackifiers and/or other additives as described above.

[1308] In another embodiment the polymer produced by this invention maybe blended with impact copolymers. Impact copolymers are defined to be ablend of isotactic PP and an elastomer such as an ethylene-propylenerubber. In a preferred embodiment the blend is a two (or more) phasesystem where the impact copolymer is a discontinuous phase and thepolymer is a continuous phase.

[1309] In another embodiment the polymer produced by this invention maybe blended with ester polymers. In a preferred embodiment the blend is atwo (or more) phase system where the polyester is a discontinuous phaseand the polymer is a continuous phase.

[1310] In a preferred embodiment the polymers of the invention describedabove are combined with metallocene polyethylenes (mPE's) or metallocenepolypropylenes (mPP's). The mPE and mPP homopolymers or copolymers aretypically produced using mono- or bis-cyclopentadienyl transition metalcatalysts in combination with an activator of alumoxane and/or anon-coordinating anion in solution, slurry, high pressure or gas phase.The catalyst and activator may be supported or unsupported and thecyclopentadienyl rings by may substituted or unsubstituted. Severalcommercial products produced with such catalyst/activator combinationsare commercially available from ExxonMobil Chemical Company in Baytown,Tex. under the tradenames EXCEED™, ACHIEVE™ and EXACT™. For moreinformation on the methods and catalysts/activators to produce such mPEhomopolymers and copolymers see WO 94/26816; WO 94/03506; EPA 277,003;EPA 277,004; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat.No. 5,240,894; U.S. Pat. No. 5,017,714; CA 1,268,753; U.S. Pat. No.5,324,800; EPA 129,368; U.S. Pat. No. 5,264,405; EPA 520,732; WO 9200333; U.S. Pat. No. 5,096,867; U.S. Pat. No. 5,507,475; EPA 426 637;EPA 573 403; EPA 520 732; EPA 495 375; EPA 500 944; EPA 570 982;WO91/09882; WO94/03506 and U.S. Pat. No. 5,055,438.

[1311] In another embodiment the olefin polymer of this invention,preferably the polypropylene homopolymer or copolymer of this invention,can be blended with another homopolymer and/or copolymer, including butnot limited to, homopolypropylene, propylene copolymerized with up to 50weight % of ethylene or a C4 to C20 alpha-olefin, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene and/or buteneand/or hexene, polybutene, ethylene vinyl acetate, low densitypolyethylene (density 0.915 to less than 0.935 g/cm³) linear low densitypolyethylene, ultra low density polyethylene (density 0.86 to less than0.90 g/cm³), very low density polyethylene (density 0.90 to less than0.915 g/cm³), medium density polyethylene (density 0.935 to less than0.945 g/cm³), high density polyethylene (density 0.945 to 0.98 g/cm³),ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylicacid, polymethylmethacrylate or any other polymers polymerizable by ahigh-pressure free radical process, polyvinylchloride, polybutene-1,isotactic polybutene, ABS resins, elastomers such as ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer elastomers such asSBS, nylons (polyamides), polycarbonates, PET resins, crosslinkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, high molecularweight polyethylene having a density of 0.94 to 0.98 g/cm³ low molecularweight polyethylene having a density of 0.94 to 0.98 g/cm³, graftcopolymers generally, polyacrylonitrile homopolymer or copolymers,thermoplastic polyamides, polyacetal, polyvinylidine fluoride and otherfluorinated elastomers, polyethylene glycols and polyisobutylene.

[1312] In a preferred embodiment the olefin polymer of this invention,preferably the polypropylene polymer of this invention, is present inthe blend at from 10 to 99 weight %, based upon the weight of thepolymers in the blend, preferably 20 to 95 weight %, even morepreferably at least 30 to 90 weight %, even more preferably at least 40to 90 weight %, even more preferably at least 50 to 90 weight %, evenmore preferably at least 60 to 90 weight %, even more preferably atleast 70 to 90 weight %.

[1313] The blends described above may be produced by mixing the two ormore polymers together, by connecting reactors together in series tomake reactor blends or by using more than one catalyst in the samereactor to produce multiple species of polymer. The polymers can bemixed together prior to being put into the extruder or may be mixed inan extruder.

[1314] Any of the above polymers, including the polymers produced bythis invention, may be functionalized. Preferred functional groupsinclude maleic acid and maleic anhydride. By functionalized is meantthat the polymer has been contacted with an unsaturated acid oranhydride. Preferred unsaturated acids or anhydrides include anyunsaturated organic compound containing at least one double bond and atleast one carbonyl group. Representative acids include carboxylic acids,anhydrides, esters and their salts, both metallic and non-metallic.Preferably the organic compound contains an ethylenic unsaturationconjugated with a carbonyl group (—C═O). Examples include maleic,fumaric, acrylic, methacrylic, itaconic, crotonic, alpha.methylcrotonic, and cinnamic acids as well as their anhydrides, esters andsalt derivatives. Maleic anhydride is particularly preferred. Theunsaturated acid or anhydride is preferably present at about 0.1 weight% to about 10 weight %, preferably at about 0.5 weight % to about 7weight %, even more preferably at about 1 to about 4 weight %, basedupon the weight of the hydrocarbon resin and the unsaturated acid oranhydride.

[1315] In a preferred embodiment the unsaturated acid or anhydriedcomprises a carboxylic acid or a derivative thereof selected from thegroup consisting of unsaturated carboxylic acids, unsaturated carboxylicacid derivatives selected from esters, imides, amides, anhydrides andcyclic acid anhydrides or mixtures thereof.

[1316] Applications

[1317] For purposes of this invention and the claims thereto, thefollowing tests are used, unless otherwise indicated.

[1318] Tensile strength, Tensile strength at break and elongation atbreak are measured by ASTM D 1708. Elongation at break is also calledstrain at break or percent elongation.

[1319] Peel strength—ASTM D-1876 (also referred to as Peel adhesion at180° peel angle, 180° peel strength, 180′ peel adhesion, T-Peelstrength, T-Peel.)

[1320] Dynamic Storage modulus also called storage modulus is G′.

[1321] Creep resistance ASTM D-2293

[1322] Rolling Ball Tack PSTC 6

[1323] Hot Shear Strength is determined by suspending a 1000 gram weightfrom a 25 mm wide strip of MYLAR polyester film coated with the polymeror adhesive formulation which is adhered to a stainless steel plate witha contact area of 12.5 mm×25 mm. The sample is placed in a ventilatedoven at 40° C. time is recorded until stress failure occurs.

[1324] Probe tack (also called Polyken probe tack) ASTM D 2979

[1325] Holding Power —PSTC 7, also called Shear adhesion or Shearstrength?.

[1326] Density—ASTM D792 at 25° C.

[1327] Gardner color ASTM D 1544-68.

[1328] SAFT is also called heat resistance.

[1329] Tensile Strength Modulus at 100% elongation and Young's Modulusare determined according to ASTM E-1876.

[1330] Luminence is the reflectance “Y” in the CIE color coordinates asdetermined by ASTM D 1925 divided by 100.

[1331] The polymer product of this invention or formulations thereof maythen be applied directly to a substrate or may be sprayed thereon,typically the polymer is molten. Spraying is defined to includeatomizing, such as producing an even dot pattern, spiral spraying suchas Nordson Controlled Fiberization or oscillating a stretched filamentlike is done in the ITW Dynafiber/Omega heads or Summit technology fromNordson, as well as melt blown techniques. Melt blown techniques aredefined to include the methods described in U.S. Pat. No. 5,145,689 orany process where air streams are used to break up filaments of theextrudate and then used to deposit the broken filaments on a substrate.In general, melt blown techniques are processes that use air to spin hotmelt adhesive fibers and convey them onto a substrate for bonding.Fibers sizes can easily be controlled from 20-200 microns by changingthe melt to air ratio. Few, preferably no, stray fibers are generateddue to the inherent stability of adhesive melt blown applicators. UnderUV light the bonding appears as a regular, smooth, stretched dotpattern. Atomization is a process that uses air to atomize hot meltadhesive into very small dots and convey them onto a substrate forbonding.

[1332] Lamination Melt Coating

[1333] The adhesives of this invention can be used in any adhesiveapplication, including but not limited to, disposables, packaging,laminates, pressure sensitive adhesives, tapes labels, wood binding,paper binding, non-wovens, road marking, reflective coatings, and thelike.

[1334] In a preferred embodiment the adhesives of this invention can beused for disposable diaper and napkin chassis construction, elasticattachment in disposable goods converting, packaging, labeling,bookbinding, woodworking, and other assembly applications. Particularlypreferred applications include: baby diaper leg elastic, diaper frontaltape, diaper standing leg cuff, diaper chassis construction, diaper corestabilization, diaper liquid transfer layer, diaper outer coverlamination, diaper elastic cuff lamination, feminine napkin corestabilization, feminine napkin adhesive strip, industrial filtrationbonding, industrial filter material lamination, filter mask lamination,surgical gown lamination, surgical drape lamination, and perishableproducts packaging.

[1335] The adhesives described above may be applied to any substrate.Preferred substrates include wood, paper, cardboard, plastic,thermoplastic, rubber, metal, metal foil (such as aluminum foil and tinfoil), metallized surfaces, cloth, non-wovens (particularlypolypropylene spun bonded fibers or non-wovens), spunbonded fibers,cardboard, stone, plaster, glass (including silicon oxide(SiO_(x))coatings applied by evaporating silicon oxide onto a filmsurface), foam, rock, ceramics, films, polymer foams (such aspolyurethane foam), substrates coated with inks, dyes, pigments, PVDCand the like or combinations thereof.

[1336] Additional preferred substrates include polyethylene,polypropylene, polyacrylates, acrylics, polyethylene terephthalate, orany of the polymers listed above as suitable for blends.

[1337] Any of the above substrates, and/or the polymers of thisinvention, may be corona discharge treated, flame treated, electron beamirradiated, gamma irradiated, microwaved, or silanized.

[1338] The adhesives produced herein, when coated in some fashionbetween two adherends, preferably perform such that the materials areheld together in a sufficient fashion compared to a standardspecification or a standard adhesive similarly constructed.

[1339] The polymer product of this invention may be used in any adhesiveapplication described in WO 97/33921 in combination with the polymersdescribed therein or in place of the polymers described therein.

[1340] The polymer product of this invention, alone or in combinationwith other polymers and or additives, may also be used to form hook andloop fasteners as described in WO 02/35956.

[1341] Characterization and Tests

[1342] Molecular weights (number average molecular weight (Mn), weightaverage molecular weight (Mw), and z-average molecular weight (Mz)) aredetermined using a Waters 150 Size Exclusion Chromatograph (SEC)equipped with a differential refractive index detector (DR1), an onlinelow angle light scattering (LALLS) detector and a viscometer (VIS). Thedetails of the detector calibrations have been described elsewhere[Reference: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley,Macromolecules, Volume 34, Number 19, 6812-6820, (2001)]; attached beloware brief descriptions of the components.

[1343] The SEC with three Polymer Laboratories PLgel 10 mm Mixed-Bcolumns, a nominal flow rate 0.5 cm³/min, and a nominal injection volume300 microliters is common to both detector configurations. The varioustransfer lines, columns and differential refractometer (the DRIdetector, used mainly to determine eluting solution concentrations) arecontained in an oven maintained at 135° C.

[1344] The LALLS detector is the model 2040 dual-angle light scatteringphotometer (Precision Detector Inc.). Its flow cell, located in the SECoven, uses a 690 nm diode laser light source and collects scatteredlight at two angles, 150 and 90°. Only the 15° output was used in theseexperiments. Its signal is sent to a data acquisition board (NationalInstruments) that accumulates readings at a rate of 16 per second. Thelowest four readings are averaged, and then a proportional signal issent to the SEC-LALLS-VIS computer. The LALLS detector is placed afterthe SEC columns, but before the viscometer.

[1345] The viscometer is a high temperature Model 150R (ViscotekCorporation). It consists of four capillaries arranged in a Wheatstonebridge configuration with two pressure transducers. One transducermeasures the total pressure drop across the detector, and the other,positioned between the two sides of the bridge, measures a differentialpressure. The specific viscosity for the solution flowing through theviscometer is calculated from their outputs. The viscometer is insidethe SEC oven, positioned after the LALLS detector but before the DRIdetector.

[1346] Solvent for the SEC experiment was prepared by adding 6 grams ofbutylated hydroxy toluene (BHT) as an antioxidant to a 4 liter bottle of1,2,4 Trichlorobenzene (TCB)(Aldrich Reagent grade) and waiting for theBHT to solubilize. The TCB mixture was then filtered through a 0.7micron glass pre-filter and subsequently through a 0.1 micron Teflonfilter. There was an additional online 0.7 micron glass pre-filter/0.22micron Teflon filter assembly between the high pressure pump and SECcolumns. The TCB was then degassed with an online degasser (Phenomenex,Model DG-4000) before entering the SEC.

[1347] Polymer solutions were prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities weremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/ml at room temperatureand 1.324 g/ml at 135° C. The injection concentration ranged from 1.0 to2.0 mg/ml, with lower concentrations being used for higher molecularweight samples.

[1348] Prior to running each sample the DRI detector and the injectorwere purged. Flow rate in the apparatus was then increased to 0.5ml/minute, and the DRI was allowed to stabilize for 8-9 hours beforeinjecting the first sample. The argon ion laser was turned on 1 to 1.5hours before running samples by running the laser in idle mode for 20-30minutes and then switching to full power in light regulation mode.

[1349] The branching index was measured using SEC with an on-lineviscometer (SEC-VIS) and are reported as g′ at each molecular weight inthe SEC trace. The branching index g′ is defined as:$g^{\prime} = \frac{\eta_{b}}{\eta_{l}}$

[1350] where η_(b) is the intrinsic viscosity of the branched polymerand η_(l) is the intrinsic viscosity of a linear polymer of the sameviscosity-averaged molecular weight (M_(v)) as the branched polymer.η_(l)=KM_(v) ^(α), K and α are measured values for linear polymers andshould be obtained on the same SEC-DRI-LS-VIS instrument as the one usedfor branching index measurement. For polypropylene samples presented inthis invention, K=0.0002288 and α=0.705 were used. The SEC-DRI-LS-VISmethod obviates the need to correct for polydispersities, since theintrinsic viscosity and the molecular weight are measured at individualelution volumes, which arguably contain narrowly dispersed polymer.Linear polymers selected as standards for comparison should be of thesame viscosity average molecular weight and comonomer content. Linearcharacter for polymer containing C2 to C 10 monomers is confirmed byCarbon-13 NMR the method of Randall (Rev. Macromol. Chem. Phys., C29(2&3), p. 285-297).

[1351] Linear character for C11 and above monomers is confirmed by GPCanalysis using a MALLS detector. For example, for a copolymer ofpropylene, the NMR should not indicate branching greater than that ofthe co-monomer (i.e. if the comonomer is butene, branches of greaterthan two carbons should not be present). For a homopolymer of propylene,the GPC should not show branches of more than one carbon atom. When alinear standard is desired for a polymer where the comomoner is C9 ormore, one can refer to T. Sun, P. Brant, R. R. Chance, and W. W.Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001) forprotocols on determining standards for those polymers. In the case ofsyndiotactic polymers, the standard should have a comparable amount ofsyndiotacticty as measured by Carbon 13 NMR.

[1352] In another embodiment the polymer produced by this invention hasa molecular weight distribution (Mw/Mn) of at least 2, preferably atleast 5, preferably at least 10, even more preferably at least 20.

[1353] In another embodiment the polymer produced may have a unimodal,bimodal, or multimodal molecular weight distribution (Mw/Mn)distribution of polymer species as determined by Size ExclusionChromatography (SEC). By bimodal or multimodal is meant that the SECtrace has more than one peak or inflection points. An inflection pointis that point where the second derivative of the curve changes in sign(e.g., from negative to positive or vice versus).

[1354] Peak melting point (Tm), peak crystallization temperature (Tc),heat of fusion and crystallinity were determined using the followingprocedure according to ASTM E 794-85. Differential scanning calorimetric(DSC) data was obtained using a TA Instruments model 2920 machine.Samples weighing approximately 7-10 mg were sealed in aluminum samplepans. The DSC data was recorded by first cooling the sample to −50° C.and then gradually heating it to 200° C. at a rate of 10° C./minute. Thesample is kept at 200° C. for 5 minutes before a second cooling-heatingcycle is applied. Both the first and second cycle thermal events arerecorded. Areas under the curves were measured and used to determine theheat of fusion and the degree of crystallinity. The percentcrystallinity is calculated using the formula, [area under the curve(Joules/gram)/B (Joules/gram)]* 100, where B is the heat of fusion forthe homopolymer of the major monomer component. These values for B areto be obtained from the Polymer Handbook, Fourth Edition, published byJohn Wiley and Sons, New York 1999. A value of 189 J/g (B) was used asthe heat of fusion for 100% crystalline polypropylene. For polymersdisplaying multiple melting or crystallization peaks, the highestmelting peak was taken as peak melting point, and the highestcrystallization peak was taken as peak crystallization temperature.

[1355] The glass transition temperature (Tg) was measured by ASTM E 1356using a TA Instrument model 2920 machine.

[1356] Polymer samples for ¹³C NMR spectroscopy were dissolved ind₂-1,1,2,2-tetrachloroethane and the samples were recorded at 125° C.using a NMR spectrometer of 75 or 100 MHz. Polymer resonance peaks arereferenced to mmmm=21.8 ppm. Calculations involved in thecharacterization of polymers by NMR follow the work of F. A. Bovey in“Polymer Conformation and Configuration” Academic Press, New York 1969and J. Randall in “Polymer Sequence Determination, Carbon-13 NMRMethod”, Academic Press, New York, 1977. The percent of methylenesequences of two in length, %(CH₂)₂, were calculated as follows: theintegral of the methyl carbons between 14-18 ppm (which are equivalentin concentration to the number of methylenes in sequences of two inlength) divided by the sum of the integral of the methylene sequences ofone in length between 45-49 ppm and the integral of the methyl carbonsbetween 14-18 ppm, times 100. This is a minimum calculation for theamount of methylene groups contained in a sequence of two or more sincemethylene sequences of greater than two have been excluded. Assignmentswere based on H. N. Cheng and J. A. Ewen, Makromol. Chem. 1989, 190,1931.

[1357] Ethylene content of a polymer can be measured as follows. A thinhomogeneous film is pressed at a temperature of about 150° C. orgreater, then mounted on a Perkin Elmer PE 1760 infraredspectrophotometer. A full spectrum of the sample from 600 cm⁻¹ to 4000cm⁻¹ is recorded and the monomer weight percent of ethylene can becalculated according to the following equation: Ethylene wt%=82.585−111.987X+30.045 X², wherein X is the ratio of the peak heightat 1155 cm⁻¹ and peak height at either 722 cm⁻¹ or 732 cm⁻¹, whicheveris higher. The concentrations of other monomers in the polymer can alsobe measured using this method.

[1358] Adhesive Testing

[1359] SAFT (modified D4498) measures the ability of a bond to withstandan elevated temperature rising at 10° F. (5.5° C.)/15 min., under aconstant force that pulls the bond in the shear mode. Bonds were formedin the manner described above (1 inch by 3 inch (2.5 cm×7.6 cm) (onKraft paper). The test specimens were suspended vertically in an oven atroom temperature with a 500 gram load attached to the bottom. Thetemperatures at which the weight fell was recorded (when the occasionalsample reached temperatures above the oven capacity >265° F. (129° C.)it was terminated and averaged in with the other samples at terminationtemperature).

[1360] Set time is defined as the time it takes for a compressedadhesive substrate construct to fasten together enough to give substratefiber tear when pulled apart, and thus the bond is sufficiently strongto remove the compression. The bond will likely still strengthen uponfurther cooling, however, it no longer requires compression. These settimes were measured by placing a molten dot of adhesive on to a filefolder substrate taped to a flat table. A file folder tab (1 inch by 3inch (2.5 cm×7.6 cm) was placed upon the dot 3 seconds later andcompressed with a 500 gram weight. The weight was allowed to sit forabout 0.5 to about 10 seconds. The construct thus formed was pulledapart to check for a bonding level good enough to produce substratefiber tear. The set time was recorded as the minimum time required forthis good bonding to occur. Standards were used to calibrate theprocess.

[1361] Once a construct has been produced it can be subjected to variousinsults in order to assess the effectiveness of the bond. Once a bondfails to a paper substrate a simple way to quantify the effectiveness isto estimate the area of the adhesive dot that retained paper fibers asthe construct failed along the bond line. This estimate is calledpercent substrate fiber tear. An example of good fiber, afterconditioning a sample for 15 hours at −12° C. and attempting to destroythe bond, would be an estimate of 80-100% substrate fiber tear. It islikely that 0% substrate fiber tear under those conditions would signala loss of adhesion.

[1362] Shore A hardness was measured according to ASTM 2240. An aircooled dot of adhesive was subjected to the needle and the deflectionwas recorded from the scale.

[1363] Dot T-Peel was determined according to ASTM D 1876, except thatthe specimen was produced by combining two 1 inch by 3 inch (2.54cm×7.62 cm) substrate cut outs with a dot of adhesive with a volumethat, when compressed under a 500 gram weight occupied about 1 squareinch of area (1 inch=2.54 cm). Once made all the specimens were pulledapart in side by side testing (at a rate of 2 inches per minute) by amachine that records the destructive force of the insult being applied.The maximum force achieved for each sample tested was recorded andaveraged, thus producing the Average Maximum Force which is reported asthe Dot T-Peel.

[1364] Adhesive Melt Viscosity (ASTM D-3236): Melt viscosity profilesare typically measured at temperatures from 120° C. to 190° C. using aBrookfield Thermosel viscometer and a number 27 spindle.

[1365] Peel Strength (modified ASTM D1876): Substrates (1×3 inches(25×76 mm)) are heat sealed with adhesive film (5 mils (130 μm)thickness) at 135° C. for 1 to 2 seconds and 40 psi (0.28 MPa) pressure.Bond specimens were peeled back in a tensile tester at a constantcrosshead speed of 2 in/min (51 mm/min). The average force required topeel the bond (5 specimens) apart is recorded.

[1366] Shear Adhesion Fail Temperature (SAFT) (modified ASTM D4498)measures the ability of the bond to withstand an elevated temperaturerising at 10° F. (5.5° C.)/15 min, under a constant force that pulls thebond in the shear mode. Bonds 1 inch by 1 inch (Kraft paper) (25 mm×25mm) were formed of adhesive by heat sealing as in procedure “(b)” abovefor 1.5 s. The test specimens were suspended vertically in an oven at32° C. with a 500 g load attached to the bottom. The temperature atwhich the weight falls is recorded. Adhesives possessing high failuretemperature are essential for the assembly of packaging goods that areoften subjected to very high temperatures during storage and shipping.

[1367] Peel Adhesion Failure Temperature (PAFT) was determined usingfollowing procedure modified according to the procedure of TAPPI T814PM-77. Two sheets of 6″×12″ Kraft paper were laminated together with aone inch strip of molten adhesive heated to 177° C. The laminated sheetwas trimmed and cut into 1-inch wide strips. These strips were placed inan oven with a 100-gram of weight hanging in a peel mode. The overtemperature increased at a rate of 30° C. per hour. The sample were hungfrom a switch that trips when the samples fail to record the temperatureof failure.

[1368] Low Temperature Substrate Fiber Tear: Kraft paper bonds areprepared as in procedure “(b)” above. The bond specimens are placed in afreezer or refrigerator to obtain the desired test temperature. Thebonds are separated by hand and a determination made as to the type offailure observed. The amount of substrate fiber tear is expressed inpercentage. “SF” indicates substrate failure.

[1369] Cloud point is determined by heating the adhesive blends to 121°C. and applying a small bead (approximately 1 gram) of the moltenadhesive to the bulb of an ASTM thermometer. The temperature at whichthe molten adhesive clouds over is then noted. These measures of cloudpoint provide an indication of a hot melt's overall compatibility, i.e.,the compatibility of the individual ingredients with each other.

[1370] Compression Molding: Plaques suitable for physical propertytesting were compression molded on a Carver hydraulic press. 6.5 g ofpolymer was molded between brass plates (0.05″ thick) lined with Teflon™coated aluminum foil. A 0.033″ thick chase with a square opening 4″×4″was used to control sample thickness. After one minute of preheat at170° or 180° C., under minimal pressure, the hydraulic load wasgradually increased to ˜10,000-15,000 lbs., at which it was held forthree minutes. Subsequently the sample and molding plates were cooledfor three minutes under ˜10,000 to 15,000 lbs. load between the watercooled platens of the press. Plaques were allowed to equilibrate at roomtemperature for a minimum of two days prior to physical propertytesting.

[1371] Unidirectional Tensile Testing: Dogbones for tensile testing werecut from compression molded plaques using a mallet handle die. Specimendimensions were those specified in ASTM D 1708. Tensile properties weremeasured on an Instron™ model 4502 equipped with a 22.48 lb. load celland pneumatic jaws fitted with serrated grip faces. Deformation wasperformed at a constant crosshead speed of 5.0 in/min with a datasampling rate of 25 points/second. Jaw separation prior to testing was0.876”, from which strains were calculated assuming affine deformation.Initial modulus, stress and strain at yield (where evident), peakstress, tensile strength at break, and strain at break were calculated.A minimum of five specimens from each plaque was tested, the resultsbeing reported as the average value. All stresses quoted were calculatedbased upon the original cross-sectional area of the specimen, taking noaccount of reduced cross-section as a function of increasing strain.

[1372] The Theological properties (G′, G″) were determined on ARESinstrument manufactured by Rheometric Scientific, Piscataway, N.J. Thepolymers were first melted and then cooled down at 1° C./min. Dynamicmoduli were recorded during the cooling, starting from a temperaturehigher than the melting point of the material by at least 30° C. down toabout 80° C. The output of the test is therefore the evolution of thestorage modulus G′, the loss modulus G″, as well as the ratio tanδ=G″/G′as a function of temperature. Measurements were made at a constantfrequency of 10 rad/s and 20 percent of strain, using a 12.5 mm diameterplate-and-plate geometry.

EXAMPLES

[1373] General

[1374] All polymerizations were performed in a liquid filled,single-stage continuous reactor using mixed metallocene catalystsystems. The reactor was a 0.5-liter stainless steel autoclave reactorand was equipped with a stirrer, a water cooling/steam heating elementwith a temperature controller, and a pressure controller. Solvents,propylene, and comonomers (such as butene and hexene), if present, werefirst purified by passing through a three-column purification system.The purification system consists of an Oxiclear column (Model #RGP-R1-500 from Labclear) followed by a 5A and a 3A molecular sievecolumns. Purification columns were regenerated periodically wheneverthere is evidence of lower activity of polymerization. Both the 3A and5A molecular sieve columns were regenerated in-house under nitrogen at aset temperature of 260° C. and 315° C., respectively. The molecularsieve material was purchased from Aldrich. Oxiclear column wasregenerated in the original manufacture. Purified ethylene from in-housesupply was fed into the manifold then the reactor through a Brookfieldmass flow controller. The ethylene was delivered as a gas solubilized inthe chilled solvent/monomer mixture. The purified solvents and monomerswere then chilled to about −15° C. by passing through a chiller beforefed into the reactor through a manifold. Solvent and monomers were mixedin the manifold and fed into reactor through a single tube. All liquidflow rates are measured using Brooksfield mass flow meters orMicro-Motion Coriolis-type flow meters.

[1375] Unless otherwise noted the catalysts compounds were obtained formAlbemarle.

[1376] The catalyst compounds used to produce semi-crystallinepolypropylene wererac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride,rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl,rac-dimethylsilylbis(indenyl)hafnium dimethyl, andrac-1,2-ethylene-bis(4,7-dimethylindenyl)hafnium dimethyl (obtained fromBoulder Scientific Company).

[1377] The catalyst compounds used to produce amorphous polypropyleneweredimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl, dimethylsilyl(tert-butylamido)(tetramethylcyclopentadienyl)titanium dimethyl(obtained from Boulder Scientific Company),[di(p-triethylsilylphenyl)methylene](cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl(produced according to the examples in U.S. Pat. No. 6,528,670)and dimethylsilyl(tetramethylcylopentadienyl)(N-1-adamantyl)titaniumdimethyl (produced according to the examples in U.S. Pat. No.5,955,625).

[1378] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride was made according to the examples in U.S. Pat. No.5,057,475. The dimethyl version was obtained by dimethylation of thedichloride version.

[1379] Rac-Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdichloride anddimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdichloride were activated with MAO (methylalumoxane).Rac-1,2-ethylenebis(4,7-dimethylindenyl)hafnium dimethyl waspreactivated with trityl tetrakis(pentafluorophenyl)borate (obtainedfrom Single-Site Catalysts, LLC). The rest of the catalysts werepreactivated with N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate(obtained from Albemarle). For catalystsystems with preactivation, the catalysts were activated with cocatalystat a molar ratio of 1:1 to 1:1.1 in 700 ml of toluene at least 10minutes prior to the polymerization reaction. The catalyst systems werediluted to a concentration of catalyst ranging from 0.2 to 1.4 mg/ml intoluene. The catalyst solution was used for all polymerization runscarried out in the same day. New batch of catalyst solution was preparedin case that more than 700 ml of catalyst solution was consumed in oneday. Each catalyst solution was pumped through separate lines. Catalystswere mixed in a manifold, and then fed into the reactor through a singleline. In methylalumoxane activated systems, 280 ml of methylalumoxane(MAO, 10 wt. % in toluene, from Albemarle) was diluted in 1000 ml oftoluene, and the solution was stored in a 5-liter stainless cylinder.Catalysts were diluted to a concentration ranging from 0.2 to 1.4 mg/mlin toluene. Each catalyst solution and the methylalumoxane solution werepumped through separate lines. Catalysts and MAO were mixed in amanifold, and then fed into the reactor through a single line. Theconnecting tube between the catalyst manifold and reactor inlet wasabout 1 meter long.

[1380] All catalyst solutions were kept in an inert atmosphere with <1.5ppm water content and fed into reactor by metering pumps. Catalyst andmonomer contacts took place in the reactor. Catalyst pumps werecalibrated periodically using toluene as the calibrating medium.Catalyst concentration in the feed was controlled through changing thecatalyst concentration in catalyst solution and/or changing in thepumping rate of catalyst solution. The pumping rate of catalyst solutionvaried in a range of 0.2 to 5 ml/minute.

[1381] As an impurity scavenger, 55 ml of tri-iso-butyl aluminum (25 wt.% in toluene, Akzo Noble) was diluted in 22.83 kilogram of hexane. Thediluted tri-iso-butyl aluminum solution was stored in a 37.9-litercylinder under nitrogen blanket. The solution was used for allpolymerization runs until about 90% of consumption, then a new batch wasprepared. Pumping rates of the tri-iso-butyl aluminum solution variesfrom polymerization reaction to reaction, ranging from 0 (no scavenger)to 4 ml per minutes.

[1382] For polymerization reactions involving alpha, omega-dienes,1,9-decadiene was diluted to a concentration ranging from 4.8 to 9.5vol. % in toluene. The diluted solution was then fed into reactor by ametering pump through a comonomer line. (The 1,9-decadiene was obtainedfrom Aldrich and was purified by first passing through alumina activatedat high temperature under nitrogen, followed by molecular sieveactivated at high temperature under nitrogen.)

[1383] The reactor was first cleaned by continuously pumping solvent(e.g., hexane) and scavenger through the reactor system for at least onehour at a maximum allowed temperature (about 150° C.). After cleaning,the reactor was heated/cooled to the desired temperature usingwater/steam mixture flowing through the reactor jacket and controlled ata set pressure with controlled solvent flow. Monomers and catalystsolutions were then fed into the reactor when a steady state ofoperation was reached. An automatic temperature control system was usedto control and maintain the reactor at a set temperature. Onset ofpolymerization activity was determined by observations of a viscousproduct and lower temperature of water-steam mixture. Once the activitywas established and system reached equilibrium, the reactor was linedout by continuing operating the system under the established conditionfor a time period of at least five times of mean residence time prior tosample collection. The resulting mixture, containing mostly solvent,polymer and unreacted monomers, was collected in a collection box afterthe system reached a steady state operation. The collected samples werefirst air-dried in a hood to evaporate most of the solvent, and thendried in a vacuum oven at a temperature of about 90° C. for about 12hours. The vacuum oven dried samples were weighed to obtain yields. Allthe reactions were carried out at a pressure of 2.41 MPa-g and in thetemperature range of 45 to 130° C.

Examples 1-4

[1384] Four samples were made withrac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl anddimethylsilyl(tetramethylcyclopentadienyl) (cyclododecylamido)titaniumdimethyl at a temperature 115° C. over a range of catalyst ratios. Thepolymerization reactions followed the general procedure described above.The detailed experimental conditions and results are presented inTable 1. TABLE 1 Example 1 2 3 4 Catalyst #1 A A A A Catalyst #1 feedrate 4.83E−06 3.66E−06 3.00E−06 2.68E−06 (mole/min) Catalyst #2 B B B BCatalyst #2 feed rate 3.64E−07 3.64E−07 3.64E−07 3.64E−07 (mole/min)Propylene feed rate 14 14 14 14 (g/min) Hexane feed rate 90 90 90 90(ml/min) Polymerization temp 115 115 115 115 (° C.) Mn (kg/mol) 19.118.2 16.4 16.9 Mw (kg/mol) 31 28.3 25.7 26.7 Mz (kg/mol) 66.1 52.4 46.953.1 g′ @ Mz 1.02 0.99 0.96 0.9 Tc (° C.) 90.5 98.8 97.7 97.1 Tm (° C.)140.5 143.2 143.8 142.8 Tg (° C.) −17.7 −10.4 −10.4 −11.3 Heat of fusion(J/g) 21.7 25.7 34.7 35.1 Viscosity @ 1540 1340 1240 798 190° C. (cps)Conversion (%) 95.3 89.6 87.1 92.8 Catalyst activity (kg 5.7 6.9 8.0 9.4polymer/g catalyst)

Examples 5-8

[1385] Four samples were made withrac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl anddimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titaniumdimethyl at a temperature of 100° C. over a range of catalyst ratio. Thepolymerization reactions followed the general procedure described above.The detailed experimental conditions and results are presented in Table2. TABLE 2 Example 5 6 7 8 Catalyst #1 F F F F Catalyst #1 feed rate4.92E−06 4.92E−06 4.92E−06 4.92E−06 (mole/min) Catalyst #2 B B B BCatalyst #2 feed rate 5.67E−07 8.50E−07 1.13E−06 1.42E−06 (mole/min)Propylene feed rate 14 14 14 14 (g/min) Hexane feed rate 90 90 90 90(ml/min) Polymerization 100 100 100 100 temperature (° C.) Mn (kg/mol)12.1 11.9 8.8 12.4 Mw (kg/mol) 29.4 30.7 26.3 28 Mz (kg/mol) 84.3 81.680.7 84.7 g′ @ Mz 0.93 0.88 0.87 0.84 Tc (° C.) 95.8 98.4 96.1 95.8 Tm(° C.) 145.2 145.7 143.3 143.0 Tg (° C.) −9.6 −10.4 −11.1 −10.0 Heat offusion (J/g) 21.4 32.4 30.0 33.0 Viscosity @ 1100 1040 840 675 190° C.(cps) Conversion (%) 88.63 91.73 68.09 77.23 Catalyst activity 6.38 6.084.18 4.42 (kg polymer/g catalyst)

Examples 9-15

[1386] Seven samples were made with dimethylsilylbis(indenyl)hafniumdimethyl anddimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl at a catalyst ratio of about 80.0 molar percent over a range oftemperatures. The polymerization reactions followed the generalprocedure described above. The detailed experimental conditions andresults are presented in Table 3. The data show that temperature hasappreciable effects on crystallinity, Mw, Mw/Mn, and level of branching.The population can also be manipulated through reaction temperaturessince the reaction kinetics of each catalyst has unique response topolymerization temperatures. TABLE 3 Example 9 10 11 12 13 14 15Catalyst #1 A A A A A A A Catalyst #1 feed 5.22E−06 5.22E−06 5.22E−065.22E−06 5.22E−06 5.22E−06 5.22E−06 rate (mole/min) Catalyst #2 C C C CC C C Catalyst #2 feed 1.31E−06 1.31E−06 1.31E−06 1.31E−06 1.31E−061.31E−06 1.31E−06 rate (mole/min) Propylene feed rate 14 14 14 14 14 1414 (g/min) Hexane feed rate 90 90 90 90 90 90 90 (ml/min) Polymerization110 105 100 95 90 85 80 temperature (° C) Mn (kg/mol) 8.5 8.2 9.8 11.122.5 26.6 30.9 Mw (kg/mol) 15.7 17.1 19.8 23.5 41.1 46.9 55.8 Mz(kg/mol) 30.6 37.9 42.2 40.4 79.8 84.8 95.5 g′ @Mz 1 0.97 0.95 0.97 0.980.97 0.98 Tc (° C.) 22.8 31.6 40.5 47.8 53.5 61.0 64.8 Tm (° C.) 74.782.3 87.4 94.3 103.3 107.7 113.7 Tg (° C.) −15.5 −13.0 −12.0 −10.0 −7.5−7.5 −6.0 Heat of fusion (J/g) 14.4 16.6 21.5 26.0 21.0 27.8 26.7Viscosity @190° C. 227 272 441 813 5280 7250 15400 (cps)

Examples 16-19

[1387] Four samples were made with rac-dimethylsilylbis(indenyl)hafniumdimethyl anddimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl at a temperature of 100° C. and various catalyst ratios. Thepolymerization reactions followed the general procedure described above.The detailed experimental conditions and results are presented in Table4. The data show that catalyst ratios have appreciable effects oncrystallinity, Mw, Mw/Mn, and level of branching. The population canalso be manipulated through reaction temperatures since the reactionkinetics of each catalyst has unique response to polymerizationtemperatures. TABLE 4 Example 16 17 18 19 Catalyst #1 A A A A Catalyst#1 feed rate 8.49E−07 8.49E−07 8.49E−07 8.49E−07 (mole/min) Catalyst #2C C C C Catalyst #2 feed rate 5.51E−07 8.26E−07 1.28E−06 1.93E−06(mole/min) Propylene feed rate 14 14 14 14 (g/min) Hexane feed rate 9090 90 90 (ml/min) Polymerization 100 100 100 100 temperature (° C.) Mn(kg/mol) 17.1 14.1 9.6 7.3 Mw (kg/mol) 28 20.7 14.3 10.6 Mz (kg/mol) 6537.6 24.9 18.2 g′ @ Mz 1.05 0.97 0.92 0.94 Tc (° C.) 61.2 55.2 30.8 28.8Tm (° C.) 107.3 97.6 76.9 64.3 Tg (° C.) −8.9 −14.5 −15.3 −14.6 Heat offusion (J/g) 29.9 31.2 19.9 7.6 Viscosity @ 1355 412 165 87 190° C.(cps) Conversion (%) 86.20 91.89 100.56 97.90 Catalyst activity 18.7416.49 13.97 10.34 (kg polymer/g catalyst)

Examples 20-34

[1388] Fifteen samples were made withrac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl anddimethylsilyl(tetramethylcyclopentadienyl) (cyclododecylamido) titaniumdimethyl catalysts, following the general procedure described above withthe exception that a small quantity of 1,9-decadiene was fed as thediolefin monomer along with propylene as the alpha-olefin monomer. Thedetailed experimental conditions and results are presented in Tables 5and 6. TABLE 5 Example 20 21 22 23 24 Catalyst #1 A A A A A Catalyst #1feed rate 6.53E−06 6.53E−06 6.53E−06 6.53E−06 6.53E−06 (mole/min)Catalyst #2 B B B B B Catalyst #2 feed rate 6.92E−07 3.64E−07 3.64E−072.19E−07 2.19E−07 (mole/min) Propylene feed rate (g/min) 14 14 14 8.3 101,9 decadiene feed rate 0.19 0.19 0.19 0.13 0.13 (ml/min) Hexane feedrate (ml/min) 90 90 90 90 90 Polymerization temperature 120 125 120 120110 (° C.) Mn (kg/mol) 15.6 14.7 14.3 — — Mw (kg/mol) 23 24.6 29.5 — —Mz (kg/mol) 55.2 64.2 85 — — g′ @Mz 0.85 0.91 0.85 — — Tc (° C.) 86.591.8 91.8 86.5 87.6 Tm (° C.) 116.6 128.7 129.7 128.8 137.6 Tg (° C.)−10.6 −11.1 −9.7 −9.4 −7.5 Heat of fusion (J/g) 31.8 32.1 26.0 17.0 19.4Viscosity @ 190° C. (cps) 721 725 1240 448 2240 Conversion (%) 93.3277.57 81.12 77.49 85.13 Catalyst activity (kg 4.00 3.54 3.70 2.15 2.85polymer/g catalyst) Example 25 26 27 28 29 Catalyst #1 A A A A ACatalyst #1 feed rate 5.22E−06 5.22E−06 5.22E−06 6.53E−06 6.53E−06(mole/min) Catalyst #2 B B B B B Catalyst #2 feed rate 7.65E−07 7.65E−077.65E−07 2.19E−07 4.74E−07 (mole/min) Propylene feed rate 14 14 14 10 14(g/min) 1,9 decadiene feed rate 0.24 2.24 0.19 0.13 0.19 (ml/min) Hexanefeed rate 90 90 90 90 90 (ml/min) Polymerization 115 117 110 125 115temperature (° C.) Mn (kg/mol) 20 23 17.3 Mw (kg/mol) 36.7 45.5 34.5 Mz(kg/mol) 111.9 104 97.1 g′ @Mz 0.68 0.75 0.75 Tc (° C.) 91.1 87.0 96.877.3 88.5 Tm (° C.) 136.6 133.7 134.2 130.0 136.3 Tg (° C.) −9.6 −10.7−9.7 −11.2 −12.4 Heat of fusion (J/g) 51.5 39.5 42.5 15.1 35.8 Viscosity@ 190° C. (cps) 880 518 1850 661 1040 Conversion (%) 92.20 89.30 96.8480.62 91.15 Catalyst activity (kg 4.72 4.57 4.96 2.70 4.07 polymer/gcatalyst)

[1389] TABLE 6 Example 30 31 32 33 34 Catalyst #1 A A A A A Catalyst #1feed rate 1.02E−06 5.22E−06 6.53E−06 6.53E−06 6.53E−06 (mole/min)Catalyst #2 B B B B B Catalyst #2 feed rate 1.13E−07 7.65E−07 4.74E−076.20E−07 3.64E−07 (mole/min) Propylene feed rate 14 14 14 14 14 (g/min)1,9 decadiene feed rate 0.19 0.24 0.19 0.19 0.19 (ml/min) Hexane feedrate 90 90 90 90 90 (ml/min) Polymerization 115 115 110 110 115temperature (° C.) Mn (kg/mol) 20.3 14.9 13.6 16.1 17.6 Mw (kg/mol) 96.234.3 30.2 30.4 36.5 Mz (kg/mol) 636.2 114.8 67.6 68.7 91.5 g′ @Mz 0.460.72 0.95 0.88 0.85 Tc (° C.) 91.4 91.8 94.3 84.4 Tm (° C.) 129.3 140.5140.6 137.2 Tg (° C.) −10.0 −11.2 −8.9 −8.2 Heat of fusion (J/g) 46.928.3 38.4 20.8 Viscosity @ 190° C. (cps) 1030 1870 1360 2470 Conversion(%) 56.38 95.32 97.29 97.24 87.82 Catalyst activity (kg 15.44 4.88 4.344.23 4.00 polymer/g catalyst)

Examples 35-39

[1390] Five samples were made with dimethylsilylbis(indenyl)hafniumdimethyl anddimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl at a catalyst ratio of 75 mol. % and over a range oftemperatures from 85 to 105° C., following the general proceduredescribed above with the exception that a small quantity of1,9-decadiene was fed as the diolefin monomer along with propylene asthe alpha-olefin monomer. The detailed experimental conditions andresults are presented in Table 7. TABLE 7 Example 35 36 37 38 39Catalyst #1 A A A A A Catalyst #1 feed rate 5.22E−06 5.22E−06 5.22E−065.22E−06 5.22E−06 (mole/min) Catalyst #2 C C C C C Catalyst #2 feed rate1.75E−06 1.75E−06 1.75E−06 1.75E−06 1.75E−06 (mole/min) Propylene feedrate 14 14 14 14 14 (g/min) 1,9 decadiene feed rate 0.24 0.24 0.24 0.240.24 (ml/min) Hexane feed rate 90 90 90 90 90 (ml/min) Polymerization105 100 95 90 85 temperature (° C.) Mn (kg/mol) 9.6 15.7 14.1 15.2 29.3Mw (kg/mol) 16.5 24.6 30 40.4 69.1 Mz (kg/mol) 33.4 48.4 70.7 103.1222.6 g′ @ Mz 0.89 0.81 0.8 0.76 0.66 Tc (° C.) 25.2 29.4 30.9 41.8 53.5Tm (° C.) 67.3 76.1 81.2 91.3 102.3 Tg (° C.) −15.4 −13.3 −13.1 −8.1−7.4 Heat of fusion (J/g) 13.4 19.5 20.9 25.7 33.3 Viscosity @ 190° C.(cps) 194 291 568 1650 5210

Examples 40-43

[1391] Four samples were made with rac-dimethylsilylbis(indenyl)hafniumdimethyl anddimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl, following the general procedure described above with theexception that a small quantity of 1,9-decadiene was fed as the diolefinmonomer along with propylene as the alpha-olefin monomer. The detailedexperimental conditions and results are presented in Table 8. TABLE 8Example 40 41 42 43 Catalyst #1 A A A A Catalyst #1 feed rate 8.49E−078.49E−07 8.49E−07 5.22E−06 (mole/min) Catalyst #2 C C C C Catalyst #2feed rate 8.26E−07 5.51E−07 5.51E−07 5.82E−07 (mole/min) Propylene feedrate 14 14 14 14 (g/min) 1,9 decadiene feed rate 0.05 0.02 0.05 0.19(ml/min) Hexane feed rate 90 90 86 90 (ml/min) Polymerization 100 95 9095 temperature (° C.) Mn (kg/mol) 10.5 16.1 23 28.3 Mw (kg/mol) 19.524.4 39.4 94.8 Mz (kg/mol) 38 44.3 71.3 455.2 g′ @ Mz 0.92 0.93 0.930.54 Tc (° C.) 47.7 53.7 71.0 37.4 Tm (° C.) 94.4 98.6 112.5 101.2 Tg (°C.) −12.3 −11.1 −24.6 −10.3 Heat of fusion (J/g) 30.8 31.6 44.6 22.4Viscosity @ 327 625 2370 — 190° C. (cps) Conversion (%) 93.80 — 98.62 —Catalyst activity 16.83 — 21.44 — (kg polymer/g catalyst)

Examples 44-47

[1392] Four samples were made usingrac-1,2-ethylene-bis(4,7-dimethylindenyl)hafnium dimethyl anddimethylsilyl-(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl at a temperature 110° C. over a range of catalyst ratios. Theconditions used for examples 44 to 47, which included diolefinincorporation, followed the general procedure described above with theexception that a small quantity of 1,9-decadiene was fed as the diolefinmonomer along with propylene as the alpha-olefin monomer. The detailedexperimental conditions and results are presented in Table 9. TABLE 9Example 44 45 46 47 Catalyst #1 A A A A Catalyst #1 feed rate 6.53E−063.79E−06 2.74E−06 2.09E−06 (mole/min) Catalyst #2 D D D D Catalyst #2feed rate 4.25E−07 4.25E−07 4.25E−07 4.25E−07 (mole/min) Propylene feedrate 14 14 14 14 (g/min) 1,9 decadiene feed rate 0.09 0.09 0.09 0.09(ml/min) Hexane feed rate 90 90 90 90 (ml/min) Polymerization 115 115115 115 temperature (° C.) Mn (kg/mol) 21.5 20 21.2 16.1 Mw (kg/mol)36.2 32.7 34 33.5 Mz (kg/mol) 100.1 95.6 123.7 128.8 Tc (° C.) 41.0 51.559.8 74.4 Tm (° C.) 94.3 97.6 103.4 109.4 Tg (° C.) −22.8 −23.8 −12.5−18.9 Heat of fusion (J/g) 4.1 6.8 11.3 15.8 Viscosity @ 2090 1750 15701230 190° C. (cps) Conversion (%) 83.58 83.95 71.84 63.10 Catalystactivity 3.80 6.26 7.08 7.78 (kg polymer/g catalyst)

Examples 48-51

[1393] Four samples were made withrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl anddimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl at a temperature of 80° C. and over a range of catalyst ratiosfrom 74 to 84 mol. %, following the general procedure described abovewith the exception that a small quantity of 1,9-decadiene was fed as thediolefin monomer along with propylene as the alpha-olefin monomer. Thedetailed experimental conditions and results are presented in Table 10.TABLE 10 Example 48 49 50 51 Catalyst #1 A A A A Catalyst #1 feed rate6.53E−06 6.53E−06 6.53E−06 6.53E−06 (mole/min) Catalyst #2 E E E ECatalyst #2 feed rate 1.23E−06 1.57E−06 1.92E−06 2.26E−06 (mole/min)Propylene feed rate 14 14 14 14 (g/min) 1,9 decadiene feed rate 0.140.14 0.14 0.14 (ml/min) Hexane rate (ml/min) 90 90 90 90 Polymerization80 80 80 80 temperature (° C.) Mn (kg/mol) 19.9 16 11.4 10 Mw (kg/mol)43.8 36.9 25.9 19.2 Mz (kg/mol) 106.3 72.3 54.5 38.8 g′ @ Mz 0.88 0.930.93 0.93 Tc (° C.) 49.0 53.3 58.6 53.1 Tm (° C.) 109.9 107.8 103.2102.0 Tg (° C.) −10.7 −7.4 −9.1 −9.6 Heat of fusion (J/g) 25.8 29.4 31.437.7 Viscosity @ 4680 2040 952 464 190° C. (cps)

Examples 52-57

[1394] Six samples were made withrac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl anddimethylsilyl-(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl at a temperature range of 80 to 95° C. and a catalyst ratio ofabout 87 molar percent, following the general procedure described abovewith the exception that (1) a small quantity of 1,9-decadiene was fed asthe diolefin monomer along with propylene as the alpha-olefin monomer;(2) A small amount of hydrogen was also fed in the reactor. The detailedexperimental conditions and results are presented in Table 11. Examples52-57 show that addition of hydrogen can effectively manipulate Mw,Mw/Mn, crystallinity, the ratio of crystalline phase to the amorphousphase, in addition to the control obtained through catalyst selectionsand process conditions such as temperatures. TABLE 11 Example 52 53 5455 56 57 Catalyst #1 A A A A A A Catalyst #1 feed rate 6.10E−06 6.10E−066.10E−06 6.10E−06 6.10E−06 6.10E−06 (mole/min) Catalyst #2 B B B B B BCatalyst #2 feed rate 2.83E−07 2.83E−07 2.83E−07 2.83E−07 1.98E−071.98E−07 (mole/min) Propylene (g/min) 14 14 14 14 14 14 1,9 decadienefeed rate 0.19 0.19 0.19 0.19 0.19 0.19 (ml/min) H2 feed rate (cc/min)50 50 50 50 70 70 Hexane feed rate 90 90 90 90 90 90 (ml/min)Polymerization 95 90 85 80 90 80 temperature (° C.) Mn (kg/mol) 12.6 1112.5 15.7 18.1 11.7 Mw (kg/mol) 27.5 43.2 42.3 85.3 34 29.8 Mz (kg/mol)72.2 127 153.4 468.3 126 99 g′ @ Mz 0.82 0.74 0.8 0.66 0.8 0.84 Tc (°C.) 95.7 95.8 97.4 97.0 98.9 97.7 Tm (° C.) 141.0 145.1 145.8 147.0144.5 145.1 Tg (° C.) −14.6 −13.3 −12.3 −9.8 −17.2 −14.8 Heat of fusion(J/g) 38.5 45.4 35.9 35.4 49.3 39.2 Viscosity @ 190° C. (cps) 668 10492148 16090 810 822

Examples 58-60

[1395] Three samples were made withrac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl anddimethylsilyl-(tetramethylcyclopentadienyl)(cyclododecylamido) titaniumdimethyl at a temperature 115° C. and a catalyst ratio of about 87 molarpercent, following the general procedure described above with thefollowing exceptions: (1) a small quantity of 1,9-decadiene was fed asthe diolefin monomer; (2) bothrac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl anddimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl catalysts were premixed and diluted in toluene, then fed intocatalyst manifold without preactivation; (3) N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate was diluted in toluene and then fedinto catalyst manifold; (4) catalyst activation started in catalystmanifold. The detailed experimental conditions and results are presentedin Table 12. Examples 58-60 demonstrate that catalysts can be activatedin-line just prior to the reactor and in reactor. TABLE 12 Example 58 5960 Catalyst #1 A A A Catalyst #1 feed rate (mole/min) 4.06E−06 2.54E−061.52E−06 Catalyst #2 B B B Catalyst #2 feed rate (mole/min) 2.95E−071.84E−07 1.11E−07 Propylene (g/min) 14 14 14 1,9 decadiene feed rate(ml/min) 0.14 0.14 0.14 Hexane feed rate (ml/min) 90 90 90Polymerization 115 115 115 temperature (° C.) Mn (kg/mol) 13.2 18.2 24.2Mw (kg/mol) 34.5 50.8 69.9 Mz (kg/mol) 99.6 169 248.6 g′ @ Mz 0.79 0.720.69 Tc (° C.) 90.6 92.9 93.0 Tm (° C.) 137.0 139.6 142.6 Tg (° C.)−10.8 −10.0 −8.7 Heat of fusion (J/g) 32.5 32.9 28.4 Viscosity @ 190° C.(cps) 1657 3170 11600 Conversion (%) 89.64 77.50 95.59 Catalyst activity(kg polymer/g 6.43 8.90 18.29 catalyst)

Examples 61-66

[1396] Six samples were made withdimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl anddimethylsilyl(tetramethylcyclopentadienyl) (cyclododecylamido) titaniumdimethyl at a temperature range of 105 to 130° C. and a catalyst ratioof about 84.6 molar percent, following the general procedure describedabove with the following exceptions: (1) a small quantity of1,9-decadiene was fed as the diolefin monomer; (2) ethylene was added tothe reactor. The detailed experimental conditions and results arepresented in Table 13. Ethylene content in the polymer was obtained fromby Fourier Transformation Infrared analysis (FTIR). TABLE 13 Example 6162 63 64 65 66 Catalyst #1 A A A A A A Catalyst #1 feed rate 1.02E−061.02E−06 1.02E−06 1.02E−06 1.02E−06 1.02E−06 (mole/min) Catalyst #2 B BB B B B Catalyst #2 feed rate 1.84E−07 1.84E−07 1.84E−07 1.84E−071.84E−07 1.84E−07 (mole/min) Propylene feed rate 20 20 20 20 20 20(g/min) 1,9 decadiene feed rate 0.186 0.186 0.186 0.186 0.186 0.186(ml/min) Ethlyene feed rate 0.2 0.2 0.2 0.2 0.2 0.2 (SLPM) Hexane feedrate 90 90 90 90 90 90 (ml/min) Polymerization 130 125 120 115 110 105temperature (° C.) Mn (kg/mol) 13.1 12.3 11.8 15.1 15.3 17.7 Mw (kg/mol)37.3 36.2 40.5 47.7 45.2 53.8 Mz (kg/mol) 149.2 122 132.1 153.9 206.8180.7 g′ @ Mz 0.67 0.65 0.63 0.61 0.56 0.56 Tc (° C.) 80.4 79.6 84.685.5 87.7 86.6 Tm (° C.) 121.8 121.9 124.6 125.2 126.1 126.2 Tg (° C.)−15.0 −15.2 −14.9 −14.8 −15.0 −15.6 Heat of fusion (J/g) 32.4 43.3 51.750.5 50.4 49.7 Viscosity @190° C. 1440 977 1090 1510 1530 1720 (cps)Ethylene content from 4.3 3.5 3 2.6 2.9 2.9 FTIR (wt. %) Conversion (%)68.11 82.57 89.87 92.79 92.18 Catalyst activity (kg 24.92 30.21 32.8833.95 33.73 polymer/g catalyst)

Examples 67-71

[1397] All these samples were made withdimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl anddimethylsilyl-(tetramethylcyclopentadienyl) (cyclododecylamido) titaniumdimethyl at a temperature range of 105 to 115° C. except example 69,following the general procedure described above with the followingexceptions: (1) a small quantity of dicyclopentadiene was used inexample 67 (The dicyclopentadiene, obtained from aldrich, was firstdissolved in toluene. The solution was then purified by passing throughalumina activated at high temperature under nitrogen, followed bymolecular sieve activated at high temperature under nitrogen.);(2)1-butene was used in examples 68 and 70; (3) 1,9-decadiene and1-hexene were fed as the diolefin monomer and comonomer, respectively inexample 71. Example 69 was made usingdimethylsilyl-(tetramethylcyclopentadienyl) (cyclododecylamido) titaniumdimethyl and rac-dimethylsily bis(2-methylindenyl)zirconium dimethylcatalysts. The detailed experimental conditions and results arepresented in Table 14. TABLE 14 Example 67 68 69 70 71 Catalyst #1 A A AA A Catalyst #1 feed rate 5.22E−06 5.22E−06 2.09E−06 5.22E−06 5.22E−06(mole/min) Catalyst #2 B B E B B Catalyst #2 feed rate 7.65E−07 7.65E−074.25E−07 7.65E−07 7.65E−07 (mole/min) Propylene feed rate 14 14 14 14 14(g/min) Comonomer dicyclopentadiene Butene-1 — Butene-1 1,9 decadieneComonomer feed rate 0.23 0.6 — 2.5 0.206 (ml/min) 1-hexene flow rate — —— — 3.29 (ml/min) Hexane feed rate 90 90 90 90 90 (ml/min)Polymerization 110 115 110 105 115 temperature (° C.) Mn (kg/mol) — —12.2 — — Mw (kg/mol) — — 30.6 — — Mz (kg/mol) — — 84.3 — — Tc (° C.) — —72.3 86.0 42.6 Tm (° C.) — — 112.1 124.8 89.8 Tg (° C.) — — −22.4 −12.3−15.2 Heat of fusion (J/g) — — 23.3 38.4 27.0 Viscosity @190° C. (cp)665 563 1420 1100 524 Conversion (%) 74.40 98.07 65.78 — 98.98 Catalystactivity (kg 3.81 5.15 8.11 — 5.77 polymer/g catalyst)

Example 72

[1398] Example 72 was carried out in a 500-ml autoclave batch reactor.125 ml of purified toluene was first added into the stainless steelautoclave reactor, followed by addition of 0.1 ml of tri-iso-butylaluminum (TIBAL) solution (25-wt. % of TIBAL diluted in 5 ml oftoluene). The mixture was then stirred and heated to 120° C. untilstable pressure. The reactor was maintained at a slightly positivepressure. In succession, 125 ml of prepurified propylene was added understirring. The reactor mixture was heated to 120° C. At this reactortemperature, 1.5 ml of the premixed and preactivated catalyst solutionwas cannulated into the reactor using nitrogen. The catalyst solutionconsists of 32 mg ofdimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl, 1.9 mg ofrac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl, and1.6 mg of dimethylsilylbis(indenyl)hafnium dimethyl, and 62.1 mg ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolvedin 50 ml of toluene. The polymerization was conducted for 15 minutes.Thereafter, the reactor was cooled down and vented to the atmosphere.The resulting mixture, containing mostly solvent, polymer and unreactedmonomers, was collected in a collection box and first air-dried in ahood to evaporate most of the solvent, and then dried in a vacuum ovenat a temperature of about 90° C. for about 12 hours. The resultingpolymer (12.79 grams) showed a peak crystallization temperature by DSCof 102.9° C., a glass transition (Tg) of −8.7° C., and a heat of fusionof 51.9 J/g. The average molecular weights, Mn/Mw/Mz, are33825/66387/267680.

Example 73-75 (Comparative)

[1399] Three samples were made withrac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl ordimethylsilyl(tetramethylcyclopentadienyl) (cyclododecylamido) titaniumdimethyl, following the general procedure described above except thatonly one catalyst was used.Rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl wasused to make isotactic polypropylene, whiledimethylsilyl(tetramethylcyclopentadienyl) (cyclododecylamido) titaniumdimethyl was used to make amorphous polypropylene. The experimentalconditions and viscosity of polymer samples are presented in Table 15.TABLE 15 Example 73 74 75 Catalyst A A B Catalyst feed rate (mol/min)5.08E−06 5.08E−06 5.67E−07 Propylene feed rate (g/min) 14 14 14 Hexanefeed rate (ml/min) 90 90 90 Polymerization temperature (° C.) 130 125110 Viscosity (cps) @ 190° C. 1132 2220 328

[1400] Several samples from the preceding experiments were analyzed todetermine their level of branching. For the purposes of this invention,the degree of branching is determined using the value of branching indexg′ at the molecular weight of Mz of the branched polymer. The resultsare presented in Tables 1 to 13.

[1401] Samples described in Example 4 and Examples 31-34 werefractionated using solvent extraction. The results are presented inTable 16. Selected fractionated fractions were analyzed usingGPC-DR1-VIS-LS and DSC. The results from these analyses are alsopresented in Table 17. The complex viscosity profiles of thefractionated fraction from sample described in Example 31 were measuredover the temperature range of 80 to 130° C., are shown in FIG. 5.

[1402] The sample described in Example 4 and its fractions extractedfrom solvent extraction were analyzed using ¹³C NMR.

[1403] Percent mm triad is measured directly from the C-13 NMR spectrum;it is assumed that the level of mm triad in the mixture depends only onthe amounts of aPP and scPP (“atactic polypropylene and semi-crystallinepolypropylene, respectively”) components in the sample. By knowing thetacticity (mm) level of the pure aPP and scPP components the proportionof each can be calculated that corresponds to the observed mm level inthe mixture. The values shown below show the percentage of isotatictriads on a whole, unfractionated polymer as well as the threefractions. The calculated data are generated by using the assumptionthat the isotactic and atactic reference polymers are indicative of thetacticities that are in the blocky polymer segments. Using the methyltriad region it is calculated that the isotactic reference polymer has94.7% mm and the atactic reference contains 13.6%. % Calculated Sample %mm Isotactic Polymer Unfractionated Polymer 68 66 Hexane Soluble 16around 2% Heptane Soluble 76 76 Heptane Insoluble 89 93

[1404] TABLE 16 Ex- ample Example Example Example Samples 31 33 32 34Hexane room temperature 29.17 42.52 55.39 74.4 solubles, wt. % Soxhlethexane soluble, 25.14 15.17 10.55 6.93 wt. % Soxhlet heptane soluble,7.88 7.1 8.53 0.44 wt. % Soxhlet heptane insoluble, 35.32 35 25.15 17.8wt. %

[1405] TABLE 17 Example 4 Hexane room Heptane Heptane temperaturesoxhlet soxhlet solubles solubles insolubles Mn (kg/mol) 6.6 10.3 16.5 —Mw (kg/mol) 14.3 30.2 31.3 — Mz (kg/mol) 32.2 58.5 53.2 — g′ @ Mz 1.160.86 0.87 — Tc (° C.) — 105.2 112.8 — Tm (° C.) — 138.2 145.2 — Tg (°C.) −11.1 — — — Heat of fusion (J/g) 0.0 68.6 108.9 — Example 31 Hexaneroom Soxhlet Soxhlet Soxhlet temperature hexane heptane heptane solublessolubles solubles insolubles Mn (kg/mol) 9.5 20.9 20.1 20.8 Mw (kg/mol)12.7 48 56.3 47.4 Mz (kg/mol) 25 131.5 148.8 150.2 g′ @ Mz 1.08 0.680.64 0.63 Tc (° C.) — 93.3 101.4 105.2 Tm (° C.) — 128.2 133.5 138.3 Tg(° C.) −11.8 −8.3 — — Heat of fusion (J/g) 0.0 52.5 66.1 70.7

[1406] The viscosity of products of Examples 12, 22 and 49 were measuredover a temperature range of 80 to 130° C. The complex viscosity profilesare shown in FIG. 1. These data demonstrate the three-zonecharacteristics described above.

[1407] Selected samples and their blends were tested for adhesiveperformance. The pure polymers were compounded with tackifiers, oil orwax and stabilizer to form hot melt adhesive blends. The properties ofthese polymers and their blends were tested against typical commerciallyavailable EVA blends from Henkel and Chief. The blending was carried outunder low shear at elevated temperature to form fluid melts. The mixingtemperatures vary from about 130 to 190° C.

[1408] Escorez™ 5637 is a hydrogenated aromatic modified resin producedfrom dicyclopentadiene feedstock, exhibiting a ring and ball softeningpoint of 130° C. available from ExxonMobil Chemical Company in Houston,Tex.

[1409] Paraflint H-1 is a Fisher-Tropsch wax exhibiting a moltenviscosity of 10 mPa sec at 250 F., available from Moore and Munger.

[1410] Aristowax 165 is a refined paraffin wax available from Frank BRoss Co in Jersey City N.J. It is isolated from petroleum and has a meltpoint of 158 to 165 F.

[1411] Henkel Hot Melt 80-8368 is a commercial hot melt made from ablend of EVA's, tackifiers, and wax available from Henkel Corp.

[1412] MAPP 40 is a maleic anhydridemodified polypropylene, having anacid number of 50, a viscosity of 300 cps at 190° C., a softening pointof 149° C., available from Chusei, USA.

[1413] Chief Hot Melt 268 is a commercial hot melt made from EVA,tackifiers, and wax available from Chief Adhesives.

[1414] KAYDOL® is a highly refined white mineral oil that consists ofsaturated aliphatic and alicyclic non-polar hydrocarbons having a pourpoint of −20° C., having a kinematic viscosity of 64 to 70 cSt at 40°C., available from Witco.

[1415] Licomont AR 504 is a maleic anhydride grafted polypropylene waxhaving an acid number of 41, a viscosity of 373 mPas at 190° C., and asoftening point of 156° C. available from Clarient.

[1416] AC 540 is an ethylene acrylic acid copolymer having an acidnumber of 40, a viscosity of 575 at 140° C. and a drop point of 105° C.available from Honeywell.

[1417] Polywax 2000 is a Polyethylene wax available from Baker PetrolitePlain BOPP (biaxially oriented polypropylene film) a 28 micron thickfilm was obtained from Mobil Films.

[1418] Corona treated BOPP (biaxially oriented polypropylene film) a 28micron thick film was obtained from Mobil Films.

[1419] Paperboard 84A is gray Poster Board 20 pt chipboard with 20%recycle fiber available from Huckster packaging and supply, Inc. inHouston, Tex.

[1420] Paperboard 84B is generic poster board clay coated news printavailable from Huckster packaging and supply, Inc. in Houston, Tex.

[1421] Cardboard 84C is generic corrugated cardboard 200 # stockavailable from Huckster packaging and supply, Inc. in Houston, Tex.Tradename Description Source Tackifiers Escorez ® 1102RM C5 tackifierExxonMobil Chemical Company Escorez ® 2203 is a low aromatic modifiedExxonMobil Chemical hydrocarbon resin having a Company narrow molecularweight distribution produced from a feed of C5, C6 and C9 olefins anddi-olefins, having a ring and ball softening point of about 95° C.Escorez ® 2393 is a highly aromatic ExxonMobil Chemical modifiedhydrocarbon resin Company produced from a feed of C5, C6 and C9 olefinsand di- olefins, having a ring and ball softening point of about 93° C.Escorez ® 2596 is a low aromatic modified ExxonMobil Chemicalhydrocarbon resin having a Company broad molecular weight distributionproduced from a feed of C5, C6 and C9 olefins and di-olefins, having aring and ball softening point of about 96° C. Escorez ® 5637 is ahydrogenated aromatic ExxonMobil Chemical modified resin producedCompany from dicyclopentadiene feedstock, exhibiting a ring and ballsoftening point of 130° C. Escorez ® 5690 is a hydrogenated aromaticExxonMobil Chemical modified resin produced Company fromdicyclopentadiene feedstock, exhibiting a ring and ball softening pointof 130° C. Oils Primol 352 Hydrogenated paraffinic oil ExxonMobilChemical Company Primol 876 Napthenic oils ExxonMobil Chemical CompanyFlexon 876 Napthenic oils ExxonMobil Chemical Company Kadol oil Refinedwhite mineral oil Witco Polymers/Adhesives Escorene UL 7720 Is anethylene vinylacetate ExxonMobil Chemical copolymer, having about 29Company weight % vinyl acetate and a melt index of 150 dg/min. NSCEasymelt Hot melt adhesive for non- National Starch, Bound wovenapplications. Brook, NJ Henkel Hot Melt 80-8368 Commercial adhesive ofHenkel Corp EVA, tackifier, and wax Chief Hot Melt 268 Commercialadhesive of Chief Adhesives EVA, tackifier, and wax Advantra 9250Commercial adhesive of Fuller ethylene/octene-1 metallocene polymers,tackifiers, and wax Tite Bond Wood Glue Water based adhesive Home Depot,Houston Texas Dap Glue Solvent based wood glue Home Depot, Houston TexasWaxes Aristowax 165 Refined petroleum wax, Frank B Ross, Jersey City,melting temperature: 158-165° F. NJ AC 8 lot 500081EQ Polyethylene waxHoneywell, New Jersey Paraflint H-1 Fisher-Tropsch wax, 10 Moore andMunger mPa @ 250° F. AR-504 Maleated PE wax acid Clarient number 41 andviscosity of 373 mPa @ 190° C. AC-540 Ethylene acrylic acid Honeywell,New Jersey copolymer having an acid number of 40 and a viscosity of 575cps @ 140° C. Polywax 2000 Polyethylene wax Baker Petrolite AC-1302PMaleated polypropylene Honeywell P-C80 Fischer Tropsch Moore and Mungerfractionated wax MAPP-40 Maleic modified Chusei, Pasadena Texaspolypropylene with acid number of 50, viscosity of 300 cps @ 190° C.Antioxidants and other additives Irganox 1010 Phenolic antioxidantCiba-Geigy Dolomite 16 mesh sand Supplied by Fordamin Company Ltd (UK)Microcarb MC 50 F calcium carbonate Supplied by Microfine Minerals Ltd(UK) Glass beads of 3 F type Glass bead Supplied by Sovitec SA (Belgium)TiO2 Lot: TR92 titanium dioxide Supplied by Hunstman Tioxide Ltd (UK)Test surfaces Metallized acrylic coated Metallized acrylic coastedGeneral Mills cardboard for cereal box Non-coated CB testliner 1250gr/m2 for vegetable Kappa, Holland trays Paperboard 84A Gray poster 20pt chipboard Huckster Packaging and with 20% recycle content Supply,Houston, TX Paperboard 84B Generic posterboard clay Huckster Packagingand coated newsprint Supply, Houston, TX Paperboard 84C Genericcorrugated Huckster Packaging and cardboard 200# stock Supply, Houston,TX Inland Paper Board High Performance box Inland Paper Board and boardPackaging Company of Rome Black White Fabric Printed stretch 100% CottonHigh Fashion Fabrics, with a Thread Count of 17 Houston Texas by 13 persquare cm, a more loosely woven fabric Formica Tabs were made fromLowe's Hardware, Houston standard sheet Formica Texas Blue fabric Tabswere made from Blue High Fashion Fabrics, Stock 038C0TP 100% HoustonTexas. Cotton, Thread Count 21 by 45 per square cm with a weight of0.022 grams per square cm, a tightly woven cotton fabric Catalog paperBook paper bound by a hot Seton Catalog melt process as determined fromexamination NWC Non-woven Coverstock, Lohmann, Germany Paratherm PT120/20 PE Polyethylene, White Tacolin Ltd, UK Opaque Micro-embossedCO/EX film (rubber treated inside), Reference #: CM001ARIE000757-CPolyester (PET) construct Polyester construct BOPP Bi-axially orientedMobil Films, Rochester, polypropylene film, 28 NY micron Corona treatedBOPP Corona treated bi-axially Mobil Films, Rochester, orientedpolypropylene NY film, 28 micron thick PP cast film construct A castfilm.

[1422] REXTAC RT 2730 is a copolymer of propylene, butene and ethylenehaving about 67.5 mole percent propylene, about 30.5 mole percent buteneand about 2 mole percent ethylene produced by Huntsman, Company. Thecopolymer has about 15 mole percent BB dyads, 43 mole percent PB dyadsand about 43 mole percent PP dyads. The melting point is 70° C. with amelting range from 25 to 116° C. the Tg is −25° C., the crystallinity isabout 7 percent, the enthalpy is 10 J/g by DSC. The Mn is 8260 the Mw is59100 and the Mz 187900 by GPC. Mw/Mn is 7.15.

[1423] REXTAC RT 2715 is a copolymer of propylene, butene and ethylenehaving about 67.5 mole percent propylene, about 30.5 mole percent buteneand about 2 mole percent ethylene produced by Huntsman, Company. Thecopolymer has about 11 mole percent BB dyads, 40 mole percent PB dyadsand about 49 mole percent PP dyads. The melting point is 76° C. with amelting range form 23 to 124° C. the Tg is −22° C., the crystallinity isabout 7 percent, the enthalpy is 11 J/g by DSC. The Mn is 6630 the Mw is51200 and the Mz 166,700 by GPC. Mw/Mn is 7.7.

[1424] All the adhesive formulations are in weight percent, unlessotherwise noted in the compositions listed in Table 18 through Table 50.TABLE 18 Applications Formulas (percent) and Performance ValuesFormulation A B C D E F Example 42 80 Escorez ™ 5637 7 7 13 10 10Paraflint H-1 13 13 7 10 Example 27 80 80 80 80 Aristowax 165 10 HenkelStandard 100 Hot Melt 80-8368 Viscosity at 190° C. 1091 870 1152 1000945 700 (cps) SAFT, F (° C.) 233 253 257 253 259 182 (112) (123) (125)(123) (126) (83) Set Time (sec.) 1.5 1.5 2 1 2.5 1 Percent SubstrateFiber 0 80 95 10 100 100 Tear Low Temperature −12° C., File folder

[1425] TABLE 19 Comparison of Blended aPP/scPP with branched aPP-g-scPPFormulation A B C D E F G Example 73 100 5 Example 74 100 39 Example 75100 39 Example 29 82 Irganox 1010 1 1 MAPP 40 5 5 Escorez ™ 5637 7 5Paraflint H-1 5 7 Henkel Standard 100 Hot Melt 80-8368 Chief Standard100 Hot Melt 268 Viscosity at 1132 2220 328 711 812 807 1055 190° C.(cps) SAFT, F (° C.) — — — 263 266 173 175 (128) (130) (78) (79) SetTime (sec.) >6 6 No 1.5-2.0 1.5 1 1.5 Adhesion Percent Substrate 100 1000 100 85 100 100 Fiber Tear Low Temperature −12° C., cardboard PercentSubstrate 0 5 0 100 100 100 100 Fiber Tear Room Temperature 20-25° C.,File Folder

[1426] TABLE 20 Comparison of branched aPP-g-scPP withpropylene/ethylene copolymers Formulation A B C D E F G H I J K Example41 100 90 90 Example 16 100 90 90 C3/C2 100 90 90 Escorez 5637 7 3 7 3 73 Paraflint H-1 3 7 3 7 3 7 Henkel Standard 100 Hot Melt 80-8368 ChiefStandard 100 Hot Melt 268 SAFT, ° F. 204 195 198 215 198 200 198 199 179171 185 Set Time (sec.) 6 5 2 >6 6 1.5 6 3 >6 2 1 Percent Substrate 0100 0 100 100 0 100 60 0 100 100 Fiber Tear Low Temperature −12° C.,Filefolder

[1427] The C3/C2 is a comparative example. The polymer was anethylene/propylene copolymer with ethylene content of about 10 wt. %.This polymer was made using rac-dimethylsilylbis(2-methyl-4-phenylindenyl) zirconium dimethyl at a polymerizationtemperature of 70° C., following the general procedure described abovefor example 1, except that only one catalyst was used. The polymer had apeak melting temperature of 95° C. and viscosity of 1368 cps at 190° C.TABLE 21 Multiple Polymer and Oil Blends of branched aPP-g-scPP PolymerFormulation A B C D E F G H I J Example 26 74 69  78  72 Example 25 7469  78  72 Example 23  5  9  5  9 Irganox 1010 1 1 1 1    1<    1<    1<   1< Kaydol Oil 10 10 10 10  5  9  5  9 Escorez ™ 5637 10 10 10 10  7 6  7  6 Paraflint H-1 5 10 5 10  5  4  5  4 Henkel Standard 100 HotMelt 80-8368 Chief Standard 100 Hot Melt 268 Viscosity, cps 315 120 525445 358 262 888 724 1002 732 190° C. SAFT, F (° C.) Set Time (sec.) 31.5 1.5 1    1.5    1.5  3  3 1.5 1.0 Percent Substrate 100 20 100 100100 100 100 100 100 100 Fiber Tear Room Temperature 20-25° C., FileFolder Percent Substrate — — — — 100 100 100 100 100 100 Fiber Tear LowTemperature 5° C., File folder

[1428] TABLE 22 Comparison of Various formulations of branchedaPP-g-scPP Formulation A B C D E F G H I Example 25 92.5 78.6 78.6Example 69 5 5 Example 29 82 84.5 82 82 Escorez ™ 5400 5 7 AR 504 5 MAPP40 5 5 2.5 5 5 Irganox 1010 .5 .4 .4 1 1 1 1 Kaydol Oil 5 5 Escorez(tm)5637 2 1.7 1.7 5 5 Paraflint H-1 5 4.3 4.3 7 7 7 5 Henkel Standard 100Hot Melt 80-8368 Chief Standard 100 Hot Melt 268 Viscosity at 790 695688 688 758 750 830 834 1050 190° C. (cps) SAFT, ° F. 263 >250 >250 265266 265 265 184 171 Set Time (sec.) 2.5 2 2 1.5 1.5 1.5 1.75 1 1.5Percent Substrate 10 98 100 75 60 90 100 100 100 Fiber Tear LowTemperature −12° C., cardboard Percent Substrate 34 100 100 100 100 100100 100 100 Fiber Tear Room Temperature 20-25° C., File Folder

[1429] TABLE 23 Hard and soft aPP-g-scPP mixes with Escorez(tm) 5400Formulation A B C D E F G H I Example 28 9 9 9 9 9 9 9 Example 17 78Example 40 78 Example 21 78 Example 20 78 Example 67 78 Example 25 78Example 26 78 Irganox 1010 1 1 1 1 1 1 1 Escorez ™ 5400 7 7 7 7 7 7 7Paraflint H-1 5 5 5 5 5 5 5 Henkel Standard 100 Hot Melt 80-8368 ChiefStandard 100 Hot Melt 268 Viscosity, cps 344 306 548 505 521 1185 404783 1090 190° C. SAFT, (° F.) Set Time (sec.) 3 3.5 3.5 2.5 1.5 >2 1.5 11.5 Percent Substrate 50 50 90 65 100 100 100 100 100 Fiber Tear LowTemperature 5° C., File Folder Percent Substrate 100 100 100 100 100 100100 100 100 Fiber Tear Room Temperature 20-25° C., File Folder Shore AHardness 74 77 54 63 76 76 76 80 85

[1430] There is no Table 24 TABLE 25 Comparison Various Wax Types withTwo Polymer Types Formulation A B C D E F G H I J K Paraflint H-1 0 10 00 0  0 10 0 0 Example 29 82 82 82 82 0  0 0 0 0 Example 62 82  82 82 8282 Escorez ™ 5637 7 7 7 7 7  7 7 7 7 Irganox 1010 1 1 1 1 1  1 1 1 1 AC540 10 10 5 Polywax 2000 10 10 5 Licowax PP 230 10  10 Henkel Standard100 Hot Melt 80-8368 Chief Standard 100 Hot Melt 268 Viscosity, cps 190°C. 820 763 1140 1254 848 977 588 691 715 765 1131 Set Time (sec.) 0.5 14 2 1.5    4+ 1 0.5 1 1 1.5 Percent Substrate 0 0 95 50 70 100 0 0 50100 100 Fiber Tear Low Temperature −12° C., cardboard Percent Substrate100 0 98 100 100 100 0 5 100 100 100 Fiber Tear Room Temperature 20-25°C., File Folder

[1431] TABLE 26 Formulating Response of butene-1 modified aPP-g-scPPFormulation A B C D E Example 68 100 93 Example 70 100 93 Escorez ™ 56372 2 Paraflint H-1 5 5 Henkel Standard 100 Hot Melt 80-8368 Viscosity@190 ° C. (cps) 563 1100 485 1140 750 Set Time (sec.) 2.5 >3 1.5 2 1Percent Substrate Fiber 100 100 88 70 100 Tear Room Temperature 20-25°C., File Folder

[1432] TABLE 27 Comparison of dicyclopentadiene modified aPP-g-scPP withand without diene Formulation A B C D E F Example 28 93 100 80 Example71 100 93 Escorez ™ 5637 2 20 2 Paraflint H-1 5 5 Henkel Standard 100Hot Melt 80-8368 Viscosity, cps 390 661 205 524 502 — 190° C. Shore AHardness 22 34 45 — — — Set Time, sec 3 4 2.5 3.5 2 1 Percent SubstrateFiber 50 80 90 80 90 90 Tear Room Temperature 20-25° C., File Folder

[1433] TABLE 28 Comparison Various aPP-g-scPP Polymer and AdhesiveBlends Formulation A B C D E F G H I J K Example 12 100 93 Example 24100 93 Example 22 100 93 88 Example 37 100 93 Escorez ™ 5637 2 2 2 4 2Paraflint H-1 5 5 5 8 5 Henkel Standard 100 Hot Melt 80-8368 ChiefStandard 100 Hot Melt 268 Viscosity, cps 190° C. 813 875 2240 1527 1240950 797 568 497 730 1027 Set Time, sec 3 3 3 3 3.5 2.5 1.5 3.5 2.5 1 1.5Percent Substrate 85 95 95 95 90 90 90 90 95 90 10 Fiber Tear RoomTemperature 20-25° C., File Folder

[1434] TABLE 29 Example Adhesive Testing on a Variety of SurfacesFormulation Blend of 78% example 29, 5% Licomont AR504, 7% Escorez 5637,5% Paraflint H-1, 5% Kaydol oil. 1% Irganox 1010 was added to the blendHenkel 80-8368 Hot Melt Maximum Maximum average Force by average Forceby Dot T-Peel Test, Dot T-Peel Test Surface (Newtons\lbs) Failure Type(Newtons\lbs) Failure Type Cardboard 84C 24.2\5.4  Substrate 16.4\3.7 Substrate Failure Failure BOPP Film 19.2\4.3  Cohesive 1.0\0.2 Complexjerking (Corona Treated) Failure PP Film plain 13.7\3.1  Several Types1.0\0.2 Complex jerking Paperboard 84B 6.0\1.3 Substrate 5.3\1.2Substrate Failure Failure Paperboard 84A 4.7\1.1 Substrate 4.6\1.0Substrate Failure Failure Aluminum foil 3.2\0.7 Cohesive 1.3\0.3Cohesive Failure Failure

Example EX 1-EX 13

[1435] The following samples were made at a temperature range of 70 to125° C., following the general procedure described above with thefollowing exceptions: (1) a small quantity of 1,9-decadiene was fed asthe diolefin monomer in Example EX1-EX3, EX5 and EX9; (2) ethylene wasused in Example EX13-EX17. The detailed experimental conditions andresults are presented in Tables 30, 31 and 32. TABLE 30 Example EX1 EX2EX3 EX4 EX5 EX6 Catalyst #1 A A A A A G Catalyst #1 feed rate 5.22E−065.88E−06 6.10E−06 3.91E−06 1.82E−06 9.89E−07 (mole/min) Catalyst #2 B EB C B C Catalyst #2 feed rate 7.65E−07 2.62E−06 2.83E−07 9.86E−079.45E−08 2.22E−07 (mole/min) Propylene feed rate 14 14 14 14 14 14(g/min) 1,9 decadiene feed rate 0.09 0.10 0.19 0.00 0.01 0.00 (ml/min)H2 (cc/min) 0 0 30 0 0 0 Hexane feed rate 90 90 90 90 90 90 (ml/min)Polymerization 95 75 70 92 100 105 temperature (° C.) Mn (kg/mol) 28.1 —15.8 — 33 — Mw (kg/mol) 63 — 58.3 — 67.7 — Mz (kg/mol) 168.3 — 203.7 —136.4 — g′ @ Mz 0.81 — 0.78 — — — Tc (° C.) 100.7 74.8 91.9 54.6 86.460.1 Tm (° C.) 146.1 113.8 148.9 103.0 149.4 102.9 Tg (° C.) −7.6 −8.2−7.1 −8.3 −6.7 −8.2 Heat of fusion (J/g) 36.5 27.8 19.3 23.9 12.5 35.8Viscosity @ 190° C. (cps) 11200 4940 10100 2940 54870 5340

[1436] TABLE 31 Example EX7 EX8 EX9 EX10 EX11 EX12 EX13 Catalyst #1 G GG G G G G Catalyst #1 feed 1.65E−06 1.65E−06 1.77E−06 2.35E−06 1.65E−069.89E−07 1.77E−06 rate (mole/min) Catalyst #2 B B B B B C B Catalyst #2feed 7.09E−08 4.72E−08 1.42E−07 5.74E−08 7.09E−08 3.70E−07 1.42E−07 rate(mole/min) Propylene feed rate 14 14 14 14 14 14 14 (g/min) Ethylenefeed rate — — — — — — 0.2 (SLPM) 1,9 decadiene feed — — 0.02 — — — —rate (ml/min) Hexane feed rate 90 90 90 90 90 90 90 (ml/min)Polymerization 110 115 125 130 120 105 110 temperature (° C.) Mn(kg/mol) 22.5 — 17.7 — — — — Mw (kg/mol) 68.6 — 35.9 — — — — Mz (kg/mol)132.4 — 67.8 — — — — g′ @ Mz — — 0.82 — — — — Tc (° C.) 96.0 81.6 82.581.0 96.5 54.2 56.9 Tm (° C.) 147.9 142.6 124.9 134.1 144.7 94.5 113.5Tg (° C.) −3.3 −2.8 −6.3 −3.9 −4.2 −10.5 −9.6 Heat of fusion (J/g) 40.715.2 37.2 17.1 40.0 32.7 21.7 Viscosity @ 190° C. 45400 47500 1180 83257957 1157 7975 (cps)

[1437] TABLE 32 Example EX14 EX15 EX16 EX17 Catalyst #1 G G G G Catalyst#1 feed 1.77E−06 1.77E−06 1.77E−06 1.77E−06 rate (mole/min) Catalyst #2B B B B Catalyst #2 feed 3.12E−07 3.12E−07 3.12E−07 3.12E−07 rate(mole/min) Propylene feed rate 14 14 10 10 (g/min) Ethylene feed rate1.5 0.8 0.8 1.5 (SLPM) Hexane feed rate 90 90 90 90 (ml/min)Polymerization 80 80 105 105 temperature (° C.) Mn (kg/mol) Mw (kg/mol)Mz (kg/mol) g′ @ Mz Tc (° C.) 28.7 58.0 19.1 — Tm (° C.) 73.7 99.3 57.6−47.8 Tg (° C.) −26.3 −19.4 −26.8 −19.5 Heat of fusion (J/g) 14.8 29.68.0 3.7 Viscosity @ 190° C. 23400 37120 495 481 (cps) Ethylene content16.9 10.7 (mole %)

[1438] Polymerization Conditions

[1439] Propylene feed at the rate of 8 lb/hr was combined with hexane at17 lb/hr to form 25 lb/hr of reactor feed solution. Tri-n-octyl aluminum(TNOA) as a 3 wt. % solution in hexane (obtained from Albemarle) wasintroduced into this stream at the rate of 0.0006 lb/hr.

[1440] Catalyst and activator entered the reactor from a separate port.The catalyst solution consisted of a mixture ofdi(p-triethylsilylphenyl)methylene](cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl (catalyst G) and rac-dimethylsilylbis(2-methyl-4-phenylindenyl) zirconium dimethyl (catalyst B), with 97molar % of catalyst G. The catalyst solution was prepared by dissolvingthe catalyst mixture in toluene to form a 0.5 wt % solution. Theactivator feed stream was made up of a 0.2 wt-% solution ofN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene. Boththe catalysts and activator were obtained from Albemarle. The catalystand activator feed lines were configured to mix in line immediatelyupstream of the reactor, with an estimated contact time of 2-4 minutes.The catalyst and activator feed rates were 0.04 g/hr and 0.1 g/hrrespectively.

[1441] The reactor feed was converted to polymer through two continuousstirred tank reactors in series. The temperatures of both reactors werecontrolled at 135° C. The reactors were operated liquid full under 530psig pressure. The residence time of the feed in each reactor was 45minutes. Conversion of propylene to polymer product was about 91%.

[1442] Molten polymer was recovered from solution via two flash stages,each with a preheater. The first stage (20 psig) polymer contained about2% solvent and the second stage (50 torr vacuum) incorporated about 800ppm volatiles. Water was injected into the second stage flash(devolatilizer) feed to quench residual catalyst and aid with solventstripping. The properties of the polymer and the finished adhesives aresummarized in Table 33. TABLE 33 Example # PP1 PP2 PP3 PP4 PP5 PP6 PP7PP8 Polymerization 132 135 135 135 135 134 133 137 temperature (° C.)Cat1 in catalyst 96 93 93 93 93 93 96 93 blend (mol %) Catalyst inreactor 3.20 4.17 4.17 4.17 4.17 4.17 4.17 3.8 feed (wppm) Propylene in28.00 29.17 29.17 29.17 29.17 28.0 28.0 30.0 reactor feed (wt %)Scavenger (wppm) 7.44 25 25 25 25 24 24 24 Quench water 1.82 0.86 0.860.86 0.62 1.4 2.8 0 (wt %) Mn (kg/mol) 18.3 17.1 13 16.7 12.3 11.4 17.318.5 Mw (kg/mol) 41.7 36.6 32.5 34.4 32.3 31.9 38.5 34.1 Mz (kg/mol)76.4 68.1 61.9 61.7 64.6 61.6 71.4 69.6 g′ @ Mz — 0.83 0.85 0.83 0.810.83 0.94 0.89 Tc (° C.) 69.2 79.8 80.6 78.4 63.8 71.8 62.8 85 Tm (° C.)131 134 136 137 130 132 137 136 Heat of fusion 15.9 25.7 30.7 28.7 3828.2 9.5 38.6 (J/g) Viscosity @ 190° C. 2300 1992 1382 1527 1211 13404235 1270 (cps)

[1443] All documents described herein are incorporated by referenceherein, including any priority documents and/or testing procedures. Asis apparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby.

We claim:
 1. A polymer comprising at least 50 mol % of one or more C3 toC40 olefins where the polymers has: a) a Dot T-Peel of 1 Newton or moreon Kraft paper; b) an Mw of 10,000 to 100,000; and c) a branching index(g′) of 0.98 or less measured at the Mz of the polymer when the polymerhas an Mw of 10,000 to 60,000, or a branching index (g′) of 0.95 or lessmeasured at the Mz of the polymer when the polymer has an Mw of 10,000to 100,000.
 2. The polymer of claim 1 wherein the polymer has: a) a DotT-Peel of 1 Newton or more on Kraft paper; b) a branching index (g′) of0.98 or less measured at the Mz of the polymer; c) a Mw of 10,000 to60,000; and d) a heat of fusion of 1 to 50 J/g.
 3. The polymer of claim1 where the polymer is a homopolypropylene or a copolymer of propyleneand up to 5 mole % ethylene having: a) an isotactic run length of 1 to30, b) a percent of r dyad of greater than 20%, and c) a heat of fusionof between 1 and 70 J/g.
 4. The polymer of claim 1 wherein the polymercomprises propylene and less than 15 mole % of ethylene.
 5. The polymerof claim 1 wherein the polymer has a melt viscosity of 7000 mPa·sec orless at 190° C.
 6. The polymer of claim 1 wherein the polymer has a meltviscosity of 5000 mPa·sec or less at 190° C.
 7. The polymer of claim 1wherein the polymer has a melt viscosity of between 250 and 6000 mPa·secat 190° C.
 8. The polymer of claim 1 wherein the polymer has a meltviscosity of between 500 and 3000 mPa·sec at 190° C.
 9. The polymer ofclaim 4 wherein the polymer has a Tg of 0° C. or less.
 10. The polymerof claim 4 wherein the polymer has a Tg of −10° C. or less.
 11. Thepolymer of claim 1 wherein the polymer has an Mw of 10,000 to 75,000 anda branching index of 0.6 or less.
 12. The polymer of claim 1 wherein thepolymer has an Mw of 10,000 to 50,000 and a branching index of 0.7 orless.
 13. The polymer of claim 1 wherein the polymer has an Mw of 10,000to 30,000 and a branching index of 0.98 or less.
 14. The polymer ofclaim 1 wherein the polymer has a branching index (g′) of 0.90 or lessmeasured at the Mz of the polymer.
 15. The polymer of claim 1 whereinthe SEC graph of the polymer is bi- or multi-modal.
 16. The polymer ofclaim 1 wherein the polymer has an amorphous content of at least 50%.17. The polymer of claim 1 wherein the polymer has a) a peak meltingpoint between 60 and 190° C.; b) a heat of fusion of 0 to 70 J/g; and c)a melt viscosity of 8000 mPa·sec or less at 190° C.
 18. The polymer ofclaim 1 wherein the polymer has: a) a Tg of −10° C. or less; b) a meltviscosity between 2000 and 6000 mPa·sec; c) a molecular weightdistribution (Mw/Mn) of at least 5; and d) a bi- or multi-modal SECgraph of the polymer.
 19. The polymer of claim 1 wherein the polymer hasa crystallinity of at least 5%.
 20. The polymer of claim 1 wherein thepolymer has 20 wt. % or more of hexane room temperature soluble fractionand 50 wt % or less of Soxhlet heptane insolubles.
 21. The polymer ofclaim 1 wherein the polymer comprises less than 3.0 mole % ethylene. 22.The polymer of claim 1 wherein the polymer comprises less than 1.0 mole% ethylene.
 23. A composition comprising the polymer of claim 1 and afunctionalized wax.
 24. A composition comprising the polymer of claim 1and a wax.
 25. A composition comprising the polymer of claim 1 and ahydrocarbon resin.
 26. The polymer of claim 1 further comprisingdiolefin.
 27. The polymer of claim 26 wherein the diolefin comprises oneor more C4 to C40 diolefins.
 28. The polymer of claim 26 wherein thediolefin is selected from the group consisting of 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene,cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene,divinylbenzene, dicyclopentadiene, polybutadienes having an Mw less than1000 g/mol, or combinations thereof.
 29. The polymer of claim 1 whereinthe polymer has an Mz/Mn of 2 to
 200. 30. The polymer of claim 1 whereinthe polymer has an Mz of 15,000 to 500,000.
 31. The polymer of claim 1wherein the polymer has a SAFT of 50 to 150° C.
 32. The polymer of claim1 wherein the polymer has a Shore A hardness of 95 or less.
 33. Thepolymer of claim 1 wherein the polymer has a set time of 5 seconds orless.
 34. The polymer of claim 1 wherein the polymer has an Mw/Mn of 2to
 75. 35. A continuous process to produce a branched olefin polymercomprising: 1) selecting a first catalyst component capable of producinga polymer having an Mw of 100,000 or less and a crystallinity of 5% orless under selected polymerization conditions; 2) selecting a secondcatalyst component capable of producing polymer having an Mw of 100,000or less and a crystallinity of 20% or more at the selectedpolymerization conditions; 3) contacting the catalyst components in thepresence of one or more activators with one or more C3 to C40 olefins;and, 4) at a temperature of greater than 100° C.; 5) at a residence timeof 120 minutes or less; 6) wherein the ratio of the first catalyst tothe second catalyst is from 1:1 to 50:1; 7) wherein the activity of thecatalyst components is at least 50 kilograms of polymer per gram of thecatalyst compounds; and wherein at least 80% of the olefins areconverted to polymer.
 36. The process of claim 35 wherein the olefincomprises propylene.
 37. The process of claim 35 wherein the firstcatalyst component comprises a non-stereospecific metallocene catalystcompound.
 38. The process of claim 35 wherein the first catalystcomponent comprises a stereospecific metallocene catalyst compound. 39.The process of claim 35 wherein the second catalyst component comprisesa stereospecific metallocene catalyst compound.
 40. The process of claim35 wherein the first catalyst component comprises one or more ofdimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido) titaniumdichloride, dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdichloride, dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(s-butylamido) titaniumdichloride, dimethylsilyl(tetramethylcyclopentadienyl)(n-butylamido)titanium dichloride,dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,diethylsilyl(tetramethylcyclopentadienyl)(cyclododecyl-amido) titaniumdichloride,diethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido) titaniumdichloride, diethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido)titanium dichloride,diethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdichloride, methylene(tetramethylcyclopentadienyl)(cyclododecyl-amido)titanium dichloride,methylene(tetramethylcyclopentadienyl)(exo-2-norbornylamido) titaniumdichloride, methylene(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dichloride,methylene(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido) titaniumdimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclododecylamido) titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclohexylamido) titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopentadienyl)(1-adamantylamido) titaniumdichloride,dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclododecylamido) titaniumdichloride,dimethylsilyl(3,4-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclohexylamido) titaniumdichloride,dimethylsilyl(3,4-dimethylcyclopentadienyl)(1-adamantylamido) titaniumdichloride,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclododecylamido)titaniumdichloride,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclohexylamido)titanium dichloride,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(1-adamantylamido)titanium dichloride,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclododecylamido)titaniumdichloride,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclohexylamido)titanium dichloride,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(1-adamantylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclododecylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(exo-2-norbornylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclohexylamido)titanium dichloride,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(1-adamantylamido)titanium dichloride,dimethylsilyl(2-tetrahydroindenyl)(cyclododecylamido) titaniumdichloride, dimethylsilyl(2-tetrahydroindenyl)(cyclohexylamido) titaniumdichloride, dimethylsilyl(2-tetrahydroindenyl)(1-adamantylamido)titanium dichloride,dimethylsilyl(2-tetrahydroindenyl)(exo-2-norbornylamido) titaniumdichloride,dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(s-butylamido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(n-butylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,diethylsilyl(tetramethylcyclopentadienyl)(cyclododecyl-amido) titaniumdimethyl,diethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido) titaniumdimethyl, diethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido)titanium dimethyl,diethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdimethyl, methylene(tetramethylcyclopentadienyl)(cyclododecyl-amido)titanium dimethyl,methylene(tetramethylcyclopentadienyl)(exo-2-norbornylamido) titaniumdimethyl, methylene(tetramethylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,methylene(tetramethylcyclopentadienyl)(1-adamantylamido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexyl-amido) titaniumdimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclododecylamido) titaniumdimethyl,dimethylsilyl(2,5-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(2,5-dimethylcyclopentadienyl)(cyclohexylamido) titaniumdimethyl, dimethylsilyl(2,5-dimethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclododecylamido) titaniumdimethyl,dimethylsilyl(3,4-dimethylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(3,4-dimethylcyclopentadienyl)(cyclohexylamido) titaniumdimethyl, dimethylsilyl(3,4-dimethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,dimethylsilyl(2-ethyl-5-methylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,dimethylsilyl(3-ethyl-4-methylcyclopentadienyl)(1-adamantylamido)titanium dimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(exo-2-norbornylamido)titanium dimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(cyclohexylamido)titanium dimethyl,dimethylsilyl(2-ethyl-3-hexyl-5-methyl-4-octylcyclopentadienyl)(1-adamantylamido)titanium dimethyl, dimethylsilyl(2-tetrahydroindenyl)(cyclododecylamido)titanium dimethyl, dimethylsilyl(2-tetrahydroindenyl)(cyclohexylamido)titanium dimethyl, dimethylsilyl(2-tetrahydroindenyl)(1-adamantylamido)titanium dimethyl, anddimethylsilyl(2-tetrahydroindenyl)(exo-2-norbornylamido) titaniumdimethyl.
 41. The process of claim 35 wherein the second catalystcomponent comprises one or more of the racemic versions of:dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dichloride,dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dimethyl,dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dichloride,dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dimethyl, dimethylsilylbis(indenyl)hafnium dimethyl, dimethylsilyl bis(indenyl)hafniumdichloride, dimethylsilyl bis(indenyl)ziconium dimethyl, dimethylsilylbis(indenyl)zirconium dichloride, the racemic isomers of:dimethylsilanediylbis(2-methylindenyl)metal dichloride;dimethylsilanediylbis(indenyl)metal dichloride;dimethylsilanediylbis(indenyl)metal dimethyl;dimethylsilanediylbis(tetrahydroindenyl)metal dichloride;dimethylsilanediylbis(tetrahydroindenyl)metal dimethyl;dimethylsilanediylbis(indenyl)metal diethyl; anddibenzylsilanediylbis(indenyl)metal dimethyl; wherein the metal can bechosen from Zr, Hf, or Ti.
 42. The process of claim 35 wherein theactivator comprises an alumoxane.
 43. The process of claim 35 whereinthe activator comprises an ionizing compound.
 44. The process of claim35 wherein the activator comprises a non-coordinating anion.
 45. Theprocess of claim 35 wherein the activator comprises one or more ofmethylalumoxane, trimethylammonium tetraphenylborate, triethylammoniumtetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, andN,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate;dicyclohexylammonium tetrakis(pentafluorophenyl)borate;triphenylphosphonium tetrakis(pentafluorophenyl)borate;tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate; andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.46. The process of claim 35 wherein the first catalyst component iscapable of polymerizing macromonomers having reactive termini; and thesecond component is capable of producing macromonomers having reactivetermini.
 47. The process of claim 35 wherein the first catalystcomponent comprises one or more ofdi(p-triethysilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconiumdichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafnium dichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)zirconium dimethyl,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafnium dimethyl,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdichloride,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)zirconiumdimethyl,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl[b,h]fluorenyl)hafniumdimethyl, and the meso forms of: dimethylsilylbis(indenyl)zirconiumdichloride, dimethylsilylbis(indenyl) zirconium dimethyl,ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconiumdimethyl, dimethylsilylbis(indenyl)hafnium dichloride,dimethylsilylbis(indenyl)hafnium dimethyl, ethylenebis(indenyl) hafniumdichloride, ethylenebis(indenyl)hafnium dimethyl,dimethylsilylbis(tetrahydroindenyl)zirconium dichloride,dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl,ethylenebis(tetrahydroindenyl)zirconium dichloride,ethylenebis(tetrahydroindenyl)zirconium dimethyl,dimethylsilylbis(tetrahydroindenyl)hafnium dichloride,dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,ethylenebis(tetrahydroindenyl)hafnium dichloride,ethylenebis(tetrahydroindenyl)hafnium dimethyl,dimethylsilylbis(2-methylindenyl)zirconium dichloride,dimethylsilylbis(2-methylindenyl) zirconium dimethyl,ethylenebis(2-methylindenyl)zirconium dichloride,ethylenebis(2-methylindenyl)zirconium dimethyl,dimethylsilylbis(2-methylindenyl)hafnium dichloride,dimethylsilylbis(2-methylindenyl) hafnium dimethyl,ethylenebis(2-methylindenyl)hafnium dichloride, andethylenebis(2-methylindenyl)hafnium dimethyl.
 48. The process of claim35 wherein the monomers comprise propylene and butene.
 49. The processof claim 35 further comprising diolefin.
 50. The process of claim 49wherein the diolefin comprises one or more C4 to C40 diolefins.
 51. Theprocess of claim 50 wherein the wherein the diolefin is selected fromthe group consisting of 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, cyclopentadiene, vinylnorbornene, norbornadiene,ethylidene norbornene, divinylbenzene, dicyclopentadiene, polybutadieneshaving an Mw less than 1000 g/mol, or combinations thereof.
 52. Theprocess of claim 49 further comprising one or more dienes selected fromthe group consisting of 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, cyclopentadiene, vinylnorbornene, norbornadiene,ethylidene norbornene, divinylbenzene, dicyclopentadiene, polybutadieneshaving an Mw less than 1000 g/mol, or combinations thereof.
 53. Theprocess of claim 35 wherein the reaction zone is a gas phase reactor.54. The process of claim 35 wherein the reaction zone is a solutionphase reactor.
 55. The process of claim 35 wherein the reaction zone isa slurry phase reactor.
 56. The process of claim 36 wherein the reactionzone is a solution phase reactor.
 57. The process of claim the catalystscomprise one or more of the following combinations (where Me equalsmethyl, Ph equals phenyl, Et equals ethyl, Cp equals cyclopentadienyl,3,6-di-t-BuFlu equals 3,8-di-tert-butylfluorenyl, 2-Me-4-PhInd equals2-methyl-4-phenylindenyl, 2-MeInd means 2-methylindenyl, c-C₁₂H₂₃ equalscyclododecyl, Me₄C₅-tetramethylcyclopentadienyl, H₄Ind equalstetrahydroindenyl, and Ind equals indenyl): (1)Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂activated with an alumoxane; (2) Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator, (2a) Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (3) Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂ andrac-Me₂Si(2-MeInd)₂ZrCl₂ activated with an alumoxane; (4)Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activatedwith a non-coordinating anion activator; (4a)Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activatedwith N,N-dimethylanilinium tetrakis(pentaflourophenyl)boron and ortriphenylcarbonium tetrakis(pentaflourophenyl)boron; (5)Me₂Si(Me₄C₅)(N-1-adamantyl)TiCl₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂activated with an alumoxane; (6) Me₂Si(Me₄C₅)(N-1-adamantyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator; (6a) Me₂Si(Me₄C₅)(N-1-adamantyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (7) Me₂Si(Me₄C₅)(N-1-adamantyl)TiCl₂and rac-Me₂Si(2-MeInd)₂ZrCl₂ activated with an alumoxane; (8)Me₂Si(Me₄C₅)(N-1-adamantyl)TiMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activatedwith a non-coordinating anion activator; (8a)Me₂Si(Me₄C₅)(N-1-adamantyl)TiMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activatedwith N,N-dimethylanilinium tetrakis(pentaflourophenyl)boron and ortriphenylcarbonium tetrakis(pentaflourophenyl)boron; (9)Me₂Si(Me₄C₅)(N-t-butyl)TiCl₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ activatedwith an alumoxane; (10) Me₂Si(Me₄C₅)(N-t-butyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator; (10a) Me₂Si(Me₄C₅)(N-t-butyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (11) Me₂Si(Me₄C₅)(N-t-butyl)TiCl₂ andrac-Me₂Si(2-MeInd) activated with an alumoxane; (12)Me₂Si(Me₄C₅)(N-t-butyl)TiMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activated witha non-coordinating anion activator; (12a) Me₂Si(Me₄C₅)(N-t-butyl)TiMe₂and rac-Me₂Si(2-MeInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (13)Me₂Si(Me₄C₅)(N-exo-norbornyl)TiCl₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂activated with an alumoxane; (14) Me₂Si(Me₄C₅)(N-exo-norbornyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator; (14a) Me₂Si(Me₄C₅)(N-exo-norbornyl)TiMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (15)Me₂Si(Me₄C₅)(N-exo-norbornyl)TiCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂activated with an alumoxane; (16) Me₂Si(Me₄C₅)(N-exo-norbornyl)TiMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with a non-coordinating anionactivator; (16a) Me₂Si(Me₄C₅)(N-exo-norbornyl)TiMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (17)(p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfCl₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂activated with an alumoxane; (18) (p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfMe₂and rac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinatinganion activator; (18a) (p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (19)(p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂activated with an alumoxane; (20) (p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfMe₂and rac-Me₂Si(2-MeInd)₂ZrMe₂ activated with a non-coordinating anionactivator; (20a) (p-Et₃SiPh)₂C(Cp)(3,8-di-t-BuFlu)HfMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (21) meso-CH₂CH₂(Ind)₂ZrCl₂ andrac-Me₂Si(H₄Ind)₂ZrCl₂ activated with an alumoxane; (22)meso-CH₂CH₂(Ind)₂ZrMe₂ and rac-Me₂Si(H₄Ind)₂ZrMe₂ activated with anon-coordinating anion activator; (22a) meso-CH₂CH₂(Ind)₂ZrMe₂ andrac-Me₂Si(H₄Ind)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (23) meso-CH₂CH₂(Ind)₂ZrCl₂ andrac-Me₂Si(2-MeInd)₂ZrCl₂ activated with an alumoxane; (24)meso-CH₂CH₂(Ind)₂ZrMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activated with anon-coordinating anion activator; (24a) meso-CH₂CH₂(Ind)₂ZrMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (25) meso-Me₂Si(Ind)₂ZrCl₂ andrac-Me₂Si(H₄Ind)₂ZrCl₂ activated with an alumoxane; (26)meso-Me₂Si(Ind)₂ZrMe₂ and rac-Me₂Si(H₄Ind)₂ZrMe₂ activated with anon-coordinating anion activator; (26a) meso-Me₂Si(Ind)₂ZrMe₂ andrac-Me₂Si(H₄Ind)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (27) meso-Me₂Si(Ind)₂ZrCl₂ andrac-Me₂Si(2-MeInd)₂ZrCl₂ activated with an alumoxane; (28)meso-Me₂Si(Ind)₂ZrMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activated with anon-coordinating anion activator; (28a) meso-Me₂Si(Ind)₂ZrMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (29) meso-Me₂Si(2-MeInd)₂ZrCl₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ activated with an alumoxane; (30)meso-Me₂Si(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activatedwith a non-coordinating anion activator; (30a) meso-Me₂Si(2-MeInd)₂ZrMe₂and rac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (31) meso-Me₂Si(2-MeInd)₂ZrCl₂ andrac-Me₂Si(2-MeInd)₂ZrCl₂ activated with an alumoxane; (32)meso-Me₂Si(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂ activated with anon-coordinating anion activator; (32a) meso-Me₂Si(2-MeInd)₂ZrMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (33) meso-CH₂CH₂(2-MeInd)₂ZrCl₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ activated with an alumoxane; (34)meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activatedwith a non-coordinating anion activator; (34a)meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activatedwith N,N-dimethylanilinium tetrakis(pentaflourophenyl)boron and ortriphenylcarbonium tetrakis(pentaflourophenyl)boron; (35)meso-CH₂CH₂(2-MeInd)₂ZrCl₂ and rac-Me₂Si(2-MeInd)₂ZrCl₂ activated withan alumoxane; (36) meso-CH₂CH₂(2-MeInd)₂ZrMe₂ andrac-Me₂Si(2-MeInd)₂ZrMe₂ activated with a non-coordinating anionactivator; (36a) meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-Me₂Si(2-MeInd)₂ZrMe₂activated with N,N-dimethylanilinium tetrakis(pentaflourophenyl)boronand or triphenylcarbonium tetrakis(pentaflourophenyl)boron; (37)meso-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ and rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂activated with an alumoxane; (38) meso-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with a non-coordinating anionactivator; (38a) meso-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ andrac-Me₂Si(2-Me-4-PhInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (39) meso-CH₂CH₂(2-Me-4-PhInd)₂ZrCl₂and rac-CH₂CH₂(2-Me-4-PhInd)₂ZrCl₂ activated with an alumoxane; (40)meso-CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂ and rac-CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂activated with a non-coordinating anion activator; (40a)meso-CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂ and rac-CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂activated with N,N-dimethylanilinium tetrakis(pentaflourophenyl)boronand or triphenylcarbonium tetrakis(pentaflourophenyl)boron; (41)meso-CH₂CH₂(2-MeInd)₂ZrCl₂ and rac-CH₂CH₂(2-MePhInd)₂ZrCl₂ activatedwith an alumoxane; (42) meso-CH₂CH₂(2-MeInd)₂ZrMe₂ andrac-CH₂CH₂(2-MeInd)₂ZrMe₂ activated with a non-coordinating anionactivator; (42a) meso-CH₂CH₂(2-MeInd)₂ZrMe₂ andrac-CH₂CH₂(2-MeInd)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (43) meso-CH₂CH₂(Ind)₂ZrCl₂ andrac-CH₂CH₂(Ind)₂ZrCl₂ activated with an alumoxane; (44)meso-CH₂CH₂(Ind)₂ZrMe₂ and rac-CH₂CH₂(Ind)₂ZrMe₂ activated with anon-coordinating anion activator; (44a) meso-CH₂CH₂(Ind)₂ZrMe₂ andrac-CH₂CH₂(Ind)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (45) meso-Me₂Si(Ind)₂ZrCl₂ andrac-Me₂Si(Ind)₂ZrCl₂ activated with an alumoxane; (46)meso-Me₂Si(Ind)₂ZrMe₂ and rac-Me₂Si(Ind)₂ZrMe₂ activated with anon-coordinating anion activator; (46a) meso-Me₂Si(Ind)₂ZrMe₂ andrac-Me₂Si(Ind)₂ZrMe₂ activated with N,N-dimethylaniliniumtetrakis(pentaflourophenyl)boron and or triphenylcarboniumtetrakis(pentaflourophenyl)boron; (47) meso-CH₂CH₂(Ind)₂ZrCl₂ andrac-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂ (4,7-Me₂Ind=4,7-dimethylindenyl) activatedwith an alumoxane; (48) meso-CH₂CH₂(Ind)₂ZrMe₂ andrac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂ activated with a non-coordinating anionactivator; (48a) meso-CH₂CH₂(Ind)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂activated with N,N-dimethylanilinium tetrakis(pentaflourophenyl)boronand or triphenylcarbonium tetrakis(pentaflourophenyl)boron; (49)meso-Me₂Si(Ind)₂ZrCl₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂ activated with analumoxane; (50) meso-Me₂Si(Ind)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂activated with a non-coordinating anion activator; (50a)meso-Me₂Si(Ind)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂ activated withN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron and ortriphenylcarbonium tetrakis(pentaflourophenyl)boron; (51)meso-CH₂CH₂(2-MeInd)₂ZrCl₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂(4,7-Me₂Ind=4,7-dimethylindenyl) activated with an alumoxane; (52)meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂ activatedwith a non-coordinating anion activator; (52a)meso-CH₂CH₂(2-MeInd)₂ZrMe₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂ activatedwith N,N-dimethylanilinium tetrakis(pentaflourophenyl)boron and ortriphenylcarbonium tetrakis(pentaflourophenyl)boron; (53)meso-Me₂Si(2-MeInd)₂ZrCl₂ and rac-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂ activatedwith an alumoxane; (54) meso-Me₂Si(2-MeInd)₂ZrMe₂ andrac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂ activated with a non-coordinating anionactivator; (54a) meso-Me₂Si(2-MeInd)₂ZrMe₂ andrac-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂ activated with such asN,N-dimethylanilinium tetrakis(pentaflourophenyl)boron and ortriphenylcarbonium tetrakis(pentaflourophenyl)boron;
 58. A compositioncomprising a homopolymer of propylene and or a copolymer of propyleneand one or more of butene, pentene, hexene, octene, nonene, and decene,wherein the copolymer comprises less than 50 mole % ethylene, andwherein the homopolymer or copolymer has a Dot T-Peel of 3 or moreNewtons; a viscosity of 8000 mPa·sec or less at 190° C.; a branchingindex (g′) of 0.85 or less measured at the Mz of the polymer; and an Mwof 100,000 or less.
 59. The composition of claim 58 wherein thehomopolymer or copolymer has an Mz of 20,000-500,000.
 60. Thecomposition of claim 58 wherein the homopolymer or copolymer has a SAFTof 60 to 130° C.
 61. The composition of claim 58 wherein the homopolymeror copolymer has a shore hardness of 60 or less.
 62. The composition ofclaim 58 wherein the homopolymer or copolymer has a set time of 2seconds or less.
 63. The composition of claim 58 wherein the homopolymeror copolymer has a branching index (g′) of 0.80 or less.
 64. Thecomposition of claim 58 wherein the homopolymer or copolymer has a heatof fusion of 20-59 J/g.
 65. A composition comprising a polymer ofpropylene, having from 0 to 5 mol % ethylene and from 0 to 40 mol % of aC5 to C12 olefin, and 0 to 10 mol % of a diene where the polymer has: a)a Dot T-Peel of 1 Newton or more; and b) an Mw of 100,000 or less; andc) a Mz/Mn of 2-200; and d) an Mw of 100,000 or less and a branchingindex of 0.5 or less, or an Mw of 75,000 or less and a branching indexof 0.6 or less, or an Mw of 50,000 or less and a branching index of 0.7or less, or an Mw of 30,000 or less and a branching index of 0.98 orless; and d) a peak melting point between 60 and 190° C., and e) aviscosity of 8000 mPa·sec or less at 190° C.; and f) a heat of fusion of70 J/g or less; and g) a Shore A Hardness (as measured by ASTM 2240) of70 or less; and h) A Shear Adhesion Fail Temperature 40 to 150° C.; andi) a set time of 5 seconds or less; and j) an Mw/Mn of 3 to 75; and k)an Mz of 20,000 to 500,000; and l) a melt index of 900 dg/min or less.66. The composition of claim 1 wherein the composition has a branchingindex (g′) of 0.90 or less measured at the Mz of the polymer.
 67. Thecomposition of claim 1 wherein the composition has a branching index(g′) of 0.85 or less measured at the Mz of the polymer.
 68. Thecomposition of claim 1 wherein the composition has a branching index(g′) of 0.80 or less measured at the Mz of the polymer.
 69. Thecomposition of claim 1 wherein the composition has a branching index(g′) of 0.75 or less measured at the Mz of the polymer.
 70. Thecomposition of claim 1 wherein the composition has a branching index(g′) of 0.70 or less measured at the Mz of the polymer.
 71. Thecomposition of claim 1 wherein the composition has a branching index(g′) of 0.65 or less measured at the Mz of the polymer.
 72. Thecomposition of claim 1 wherein the composition has a branching index(g′) of 0.60 or less measured at the Mz of the polymer.
 73. Thecomposition of claim 1 wherein the composition has a branching index(g′) of 0.55 or less measured at the Mz of the polymer.
 74. Thecomposition of claim 1 wherein the composition has a branching index(g′) of 0.50 or less measured at the Mz of the polymer.
 75. A continuousprocess to prepare an adhesive comprising: 1) combining monomer,solvent, catalyst and activator in a reactor system, 2) withdrawingpolymer solution from the reactor system, 3) removing at least 10%solvent from the polymer solution, 4) quenching the reaction, 5)devolatilizing the polymer solution to form molten polymer, 6) combiningthe molten polymer and one or more additives in a static mixer, 7)removing the polymer combination from the static mixer, and 8)pelletizing or drumming the polymer combination.
 76. A continuousprocess to produce a branched olefin polymer comprising: 1) selecting afirst catalyst component capable of producing a polymer having an Mw of80,000 or less and a crystallinity of 15% or less under selectedpolymerization conditions; 2) selecting a second catalyst componentcapable of producing polymer having an Mw of 80,000 or less and acrystallinity of 50% or more at the selected polymerization conditions;3) contacting the catalyst components in the presence of one or moreactivators with propylene and one or more C4 to C20 olefins, and,optionally one or more C4 to C20 diolefins; 4) at a temperature ofgreater than 105C; 5) at a residence time of 90 minutes or less; 6)wherein the ratio of the first catalyst to the second catalyst is from1:1 to 20:1; 7) wherein the activity of the catalyst components is atleast 100 kilograms of polymer per gram of the catalyst compounds; andwherein at least 80% of the olefins are converted to polymer.
 77. Theprocess of claim 76 wherein: a) the olefins comprise propylene and oneor more of butene, pentene, hexene, heptene, octene; nonene, decene,dodecene; and b) the temperature is greater than 110° C.; and c) theresidence time is 120 minutes or less; and d) the ratio of the firstcatalyst to the second catalyst is from 1:1 to 1:10.
 78. The process ofclaim 76 wherein the diolefin is selected from the group consisting of1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, cyclopentadiene, vinylnorbornene, norbornadiene,ethylidene norbornene, divinylbenzene, dicyclopentadiene, polybutadieneshaving an Mw less than 1000 g/mol, butadiene, pentadiene, hexadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene, or combinations thereof.
 79. The process of claim 76wherein the olefin comprises propylene and one or more of butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methyl-pentene-1,3-methyl pentene-1, and 3,5,5-trimethyl-hexene-1. 80.A continuous process to make an adhesive comprising 1) selecting a firstcatalyst component capable of producing a polymer having an Mw of100,000 or less and a crystallinity of 20% or less under selectedpolymerization conditions; 2) selecting a second catalyst componentcapable of producing polymer having an Mw of 100,000 or less and acrystallinity of 40% or more at the selected polymerization conditions;3) contacting, in a solvent and in a reaction zone under the selectedpolymerization conditions, the catalyst components in the presence ofone or more activators with one or more C3 to C40 olefins, and,optionally one or more diolefins; 4) at a temperature of greater than100° C.; 5) at a residence time of 120 minutes or less; 6) wherein theratio of the first catalyst to the second catalyst is from 1:1 to 50:1;7) wherein the activity of the catalyst components is at least 50kilograms of polymer per gram of the catalyst compounds; and wherein atleast 80% of the olefins are converted to polymer; 8) withdrawingpolymer solution from the reaction zone; 9) removing at least 10%solvent from the polymer solution; 10) quenching the reaction; 11)devolatilizing the polymer solution to form molten polymer; 12)combining the molten polymer and one or more additives in a staticmixer; 13) removing the polymer combination from the static mixer; and14) pelletizing or drumming the polymer combination.
 81. A polymercomprising one or more C3 to C40 olefins, optionally one or morediolefins, and less than 1 mole % of ethylene where the polymers has: a)a Dot T-Peel of 1 Newton or more; and b) a branching index (g′) of 0.95or less measured at the Mz of the polymer; and c) an Mw of 100,000 orless; and wherein the polymer has at least 2 mol % (CH₂)₂ units.
 82. Thepolymer of claim 81 wherein the polymer has at least 4 mol % (CH₂)₂units.
 83. The polymer of claim 81 wherein the polymer has at least 6mol % (CH₂)₂ units.
 84. The polymer of claim 81 wherein the polymer hasat least 8 mol % (CH₂)₂ units.
 85. The polymer of claim 81 wherein thepolymer has at least 10 mol % (CH₂)₂ units.
 86. The polymer of claim 81wherein the polymer has at least 15 mol % (CH₂)₂ units.
 87. The polymerof claim 81 wherein the polymer has at least 20 mol % (CH₂)₂ units. 88.A polymer comprising one or more C3 to C40 olefins, optionally one ormore diolefins, and having between 1 and mole % of ethylene where thepolymers has: a) a Dot T-Peel of 1 Newton or more; and b) a branchingindex (g′) of 0.95 or less measured at the Mz of the polymer; and c) anMw of 100,000 or less; and wherein the polymer has at least 2+X mol %(CH₂)₂ units, where X is the mole % ethylene.
 89. The polymer of claim88 wherein the polymer has at least 4+X mol % (CH₂)₂ units.
 90. Thepolymer of claim 88 wherein the polymer has at least 6+X mol % (CH₂)₂units.
 91. The polymer of claim 88 wherein the polymer has at least 8+Xmol % (CH₂)₂ units.
 92. The polymer of claim 88 wherein the polymer hasat least 10+X mol % (CH₂)₂ units.
 93. The polymer of claim 88 whereinthe polymer has at least 15+X mol % (CH₂)₂ units.
 94. The polymer ofclaim 88 wherein the polymer has at least 20+X mol % (CH₂)₂ units.
 95. Apolymer comprising one or more C3 to C40 olefins, optionally one or morediolefins, and less than 50 mole % of ethylene where the polymers has:a) a Dot T-Peel of 5 Newton or more; and b) a branching index (g′) of0.95 or less measured at the Mz of the polymer; and c) an Mw of 100,000or less.
 96. The composition of claim 1 further comprising one orhydrocarbon resins selected from the group consisting of aliphatichydrocarbon resins, aromatic modified aliphatic hydrocarbon resins,hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gumrosins, gum rosin esters, wood rosins, wood rosin esters, tall oilrosins, tall oil rosin esters, polyterpenes, aromatic modifiedpolyterpenes, terpene phenolics, aromatic modified hydrogenatedpolycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenatedaliphatic aromatic resins, hydrogenated terpenes and modified terpenes,and hydrogenated rosin esters.
 97. The composition of claim 1 furthercomprising hydrocarbon resin present at 1 weight % to about 80 weight %.98. The composition of claim 1 further comprising hydrocarbon resinpresent at 2 weight % to about 40 weight %.
 99. The composition of claim1 further comprising hydrocarbon resin present at 3 weight % to 30weight %.
 100. The composition of claim 1 further comprising hydrocarbonresin present at 1 weight % to about 80 weight % selected from the groupconsisting of: C5/C6 terpene resins, styrene terpenes, alpha-methylstyrene terpene resins, C9 terpene resins, aromatic modified C5/C6,aromatic modified cyclic resins, aromatic modified dicyclopentadienebased resins, resins obtained from the cationic polymerization ofcompositions containing one or more of the following monomers: C5diolefins; C5 olefins; C6 olefins, C9 vinylaromatics; cyclics; and orterpenes; resins obtained by the thermal polymerization ofdicyclopentadiene, and/or the thermal polymerization of dimers oroligomers of cyclopentadiene and/or methylcyclopentadiene, optionallywith vinylaromatics.
 101. A composition comprising the polymer of claim1 and having less than 5% hydrocarbon resin.
 102. A compositioncomprising the polymer of claim 1 and having less than 3% hydrocarbonresin.
 103. A composition comprising the polymer of claim 1 and havingless than 1% hydrocarbon resin.
 104. A polymer comprising one or more C3to C40 olefins where the polymers has: a) a Dot T-Peel between 1 and10,000 Newtons; and b) a branching index (g′) of 0.95 or less measuredat the Mz of the polymer; and c) an Mw of 100,000 or less.
 105. Thepolymer of claim 104 wherein the polymer has a Dot T-Peel of between 3and 4000 Newtons.
 106. The polymer of claim 104 wherein the polymer hasa Dot T-Peel of between 5 and 3000 Newtons.
 107. The polymer of claim104 wherein the polymer has a Dot T-Peel of between 10 and 2000 Newtons.108. The process of claim 37 wherein the second catalyst componentcomprises one or more of: dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethylsiladiyl(2-iso-propyl, 4-[31,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-butyl,4-[31,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-propyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl; dimethylsiladiyl(2-iso-propyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride; dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl) ₂hafnium dichloride;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-methyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dichloride;9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-methyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl) ₂hafnium dimethyl;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dimethyl;9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloridedimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-iso-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride; dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-iso-butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride; dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl) ₂hafnium dichloride;dimethylsiladiyl(2-tert-butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyldimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-isobutyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl) ₂hafnium dimethyl;dimethylsiladiyl(2-iso-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl; dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene; dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-ethyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂1,4-1,4-diphenyl-1,3-butadiene; 9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ηl-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloridedimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η²-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene; dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-n-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene; dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl) η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-n-butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂114-1,4-diphenyl-1,3-butadiene; dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;dimethylamidoborane(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl; dimethylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyldimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloridediisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂1′-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-tert-butyl,4-[31,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-n-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)2 η⁴-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-n-butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-iso-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyldiisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloridebis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethylbis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl; orbis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl.
 109. A polymercomprising one or more C3 to C40 olefins and less than 1 mole % ofethylene where the polymer has: a) a Dot T-Peel of 1 Newton or more; andb) a branching index (g′) of 0.95 or less measured at the Mz of thepolymer; and c) an Mw of 100,000 or less; and the polymer has anamorphous component which contains at least 3 mol % (CH₂)₂ units. 110.The polymer of claim 109 where the amorphous component contains at least6 mol % (CH₂)₂ units.
 111. The polymer of claim 109 where the amorphouscomponent contains at least 10 mol % (CH₂)₂ units.
 112. The polymer ofclaim 109 where the amorphous component contains at least 15 mol %(CH₂)₂ units.
 113. The polymer of claim 109 where the amorphouscomponent contains at least 20 mol % (CH₂)₂ units.
 114. A polymercomprising one or more C3 to C40 olefins and between 1 and 5 mole % ofethylene where the polymer has: a) a Dot T-Peel of 1 Newton or more; andb) a branching index (g′) of 0.95 or less measured at the Mz of thepolymer; and c) an Mw of 100,000 or less; and the polymer has anamorphous component which contains at least 3+X mol % (CH₂)₂ units,where X is the mol % ethylene in the polymer.
 115. The polymer of claim114 where the amorphous component contains at least 6+X mol % (CH₂)₂units.
 116. The polymer of claim 114 where the amorphous componentcontains at least 10+X mol % (CH₂)₂ units.
 117. The polymer of claim 114where the amorphous component contains at least 15+X mol % (CH₂)₂ units.118. The polymer of claim 114 where the amorphous component contains atleast 20+X mol % (CH₂)₂ units.